超临界水热制备LiFePO4及煅烧碳包覆改性研究

本文以FeSO_4、H_3PO_4和LiOH为原料,采用超临界水热过程制备了亚微米级LiFePO_4颗粒.在此基础上,为了提升制备的LiFePO_4正极材料的物理和电化学性能,对其进行了后续煅烧碳包覆改性研究.同时,通过XRD、SEM、充放电测试、CV和EIS测试手段,对LiFePO_4正极材料改性前后的结构、形貌和电化学性能进行了表征.结果表明:后续固相煅烧碳包覆改性能够显著改善LiFePO_4的结晶性能,减小颗粒粒径,降低电荷传递阻抗,以及大幅度地提升放电容量和循环性能;以PVP为模板剂、蔗糖为碳源,700℃煅烧1 h得到的LiFePO_4/C颗粒粒径小、分布均一,室温0.2 C倍率的首圈放电比容量为153.1 mAh/g,1 C倍率充放电时,放电比容量可保持在144.2 mAh/g,1 C循环50次,容量保持率达到97.1%.     

钠离子电池用膨胀石墨的电化学法制备及性能探究

为了探究膨胀石墨的储钠性能,利用电化学法制备了膨胀石墨,采用XRD对其结构进行了表征,并利用恒电流充放电、循环伏安(CV)、电化学阻抗谱(EIS)对其储钠性能进行了分析。结果表明,鳞片石墨经过电化学氧化再经过高温瞬时膨胀之后,层间距略微增大,但依然保持着石墨的层状结构。以二乙二醇二甲醚(DEGDME)为电解液,膨胀石墨对钠离子表现出较好的嵌/脱钠容量、倍率性能和循环性能:当电流密度为700mA/g时,其可逆比容量为110.9mAh/g,是10mA/g时容量的66.8%。在100mA/g电流密度下循环100次时,其第100次循环时的放电比容量为154.8 mAh/g,第一次循环时的放电比容量为134.8 mAh/g,容量保持率为114.8%。通过PITT测试,得出钠离子在膨胀石墨中的化学扩散系数为DNa+=7.7×10-8 cm2/s。     

正四棱柱状LiFePO4/Ag/RGO三元复合材料的制备

以乙二醇作溶剂,采用溶剂热法,调节不同pH,合成了不同形貌的磷酸铁锂(LiFePO_4)纳米材料。对其进行银(Ag)/氧化石墨烯(GO)的复合,制得正四棱柱状LiFePO_4/Ag/RGO三元复合材料,并对其进行了测试。结果表明,在不同pH条件下合成的LiFePO_4/Ag/RGO三元复合材料均为橄榄石晶型LiFePO_4,在pH=10,0.2C倍率放电条件下,LiFePO_4/Ag/RGO三元复合材料的放电比容量达到154.06mAh/g,1C条件下50次循环容量保持率在96%以上。     

核壳结构TiC/Co_3O_4纳米线的制备及其电化学储锂性能

以棉纤维为碳源和模板,采用生物模板法成功合成制备直径约100~150nm、长度几至十几微米的TiC纳米线,进而通过水热反应在其表面均匀沉积Co_3O_4纳米微粒,所构建的核壳结构TiC/Co_3O_4纳米线具有良好的循环稳定性和高倍率性能。在50mA/g电流密度下循环的第2次、第50次放电容量分别为824.3mAh/g和753.7mAh/g;在倍率性能测试中,当电流密度回到50mA/g时,可逆放电容量为1060.4mAh/g,高于起始的1048.2mAh/g。     

碳芯结构LiFePO_4/C复合材料的表征及电化学性能

采用环氧树脂为碳源制备出碳芯结构LiFePO4/C复合材料.利用X射线衍射、扫描电镜、透射电镜和X光电子能谱等分别对复合材料的晶体结构、表面形貌及表面成分进行表征,采用恒电流充放电和电化学阻抗方法研究试样的电化学性能.实验结果表明:碳芯结构复合材料是由无定形碳线和纳米LiFePO4颗粒组成.碳芯结构LiFePO4/C复合材料在15mA/g的电流密度下,首次放电容量达到166mAh/g,当电流密度增加到750mA/g,放电容量高达131mAh/g,经过50次循环后,容量保持率高达99.2%.     

碳包覆的磷/石墨烯复合材料的制备及其储锂性能研究

以纳米黑磷和氧化石墨烯为原料,通过高温热处理的方法合成了碳包覆的磷/石墨烯复合材料,通过XRD、Raman、FT-IR、XPS及SEM对该复合材料进行表征。电化学性能测试表明,在100mA/g的电流密度下,制备的复合材料首次充电比容量为530mAh/g,循环50次后比容量仍然保持在492mAh/g,容量保持率为92.8%,表现出优异的电化学性能。     

新型负极材料CrNbO_4的电化学性能研究及球磨改性

采用高温固相法制备CrNbO_4,并首次研究其作为锂离子电池负极材料的电化学性能。使用X射线衍射分析(XRD)、扫描电子显微镜(SEM)、充放电测试、循环伏安(CV)测试和电化学交流阻抗测试(EIS)对材料的结构、形貌和电化学性能进行表征。样品CrNbO_4在0.001~3.0V电压区间,电流密度为16 mA/g时,充放电50次后放电容量可以保持在63.5mAh/g。通过球磨,CrNbO_4的首次放/充电容量由212.9/100.9 mAh/g提高到572.3/343.5mAh/g,同时电流密度提高10倍,充放电50次后改性样品的放电容量仍可维持81.3mAh/g,有效提高了电化学性能。     

葡萄糖对微波水热合成正极材料LiFePO_4的结构和性能的影响

以FeSO_4·7H_2O,LiOH·H_2O和H_3PO_4为原料,葡萄糖为改性剂,采用微波水热法合成具有正交晶系橄榄石结构的LiFePO_4/C复合材料。借助XRD,SEM,EDS和电化学性能测试等分析,研究葡萄糖对产物组成、结构、微观形貌和电化学性能的影响。结果表明:葡萄糖改性后,LiFePO_4结构中Fe,P和O原子间的结合增强,颗粒尺寸减小,表面有碳层包覆,电化学性能提高。LiFePO4/C在0.1C倍率下的首次放电比容量为125.6mAh/g;1.0C倍率下的首次放电比容量为106.2mAh/g,30次循环后的容量保持率为91.3%。     

VO_2/rGO复合材料的制备及作为高容量锂离子电池负极的研究

采用简易的一步水热法实现了VO_2和rGO的有效复合,通过XRD、SEM、Raman等手段对复合材料的结构和形貌进行了表征,评估了该材料作为锂离子电池负极的电化学性能。结果显示,VO_2为片状形貌,氧化石墨烯在水热反应中被还原,与VO_2片形成了良好的复合结构。电化学数据显示,在100 mA/g电流密度下,VO_2/rGO复合材料可逆容量高达621.8mAh/g,远高于石墨的理论容量(372mAh/g)。在300mA/g电流密度下,该材料在100次循环后容量保持在384mAh/g。更重要的是,在2 000mA/g电流密度下,300次循环后容量仍维持在256mAh/g,容量保持率接近100%。基于rGO良好的导电性能以及VO_2与rGO的协同作用,制备的VO_2/rGO复合材料体现了较高的可逆比容量和良好的倍率性能及循环稳定性能,是一种具有前景的锂离子电池负极材料。     

交联网状结构聚硅氧烷类固体电解质的制备及电化学性能研究

采用硅氢加成交联的方法制备了具有网络结构的聚硅氧烷固体电解质,采用热重分析、交流阻抗、线性扫描伏安法对电解质进行表征,考察了锂盐含量以及温度对电解质离子电导率的影响。结果表明:电解质在常温下电导率最大可以达到1.74×10~(-4)S/cm,热稳定性在220℃达到最佳,电化学窗口可达到5V(vs.Li/Li~+);电解质与锂电极的稳定性较好。将聚合物电解质组装成LiFePO_4/SPE/Li锂离子电池,电池在0.07C倍率下,充放电比容量达到160mAh/g,充放电平台在3.45V左右;在0.15C倍率下,电池循环26圈后,电池充放电比容量保持在134mAh/g,库伦效率保持在98%以上。     

Doping Effects on Electronic Conductivity and Electrochemical Performance of LiFePO4

Olivine-structured pure LiFePO₄ and doped Li(M, Fe)PO₄ (M=La, Ce, Nd, Mn, Co, Ni) have been synthesized by a solvothermal method. X-ray diffraction and field emission scanning electron microscopy analyses indicate that the as-prepared LiFePO₄ is well-crystallized nanopowders without any detectable impurity phases. The electronic conductivity of LiFePO₄ is enhanced by around 1-3 orders by doping. It was found that doping alone is not sufficient for the high-rate performance of LiFePO₄ and surface coating with such as carbon should be needed. The best dopant for LiFePO4 is Nd among those studied in the present work. Accordingly, doping with 1 mol fraction Nd leads to an increase in 70 mAh/g at 0.1 C for the hydrothermally synthesized sample and 50 mAh/g at 1.0 C after carbon-coating in comparison with the undoped samples.     

Synthesis of ribbon type carbon nanostructure using LiFePO4 catalyst and their electrochemical performance

Ribbon type of carbon nanostructure has been synthesized by chemical vapor deposition using a new catalyst (LiFePO₄) introduced for the first time and its electrochemical behavior has been determined from charge/discharge characteristics. The synthesized material characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and by Raman spectroscopy confirms the graphitic structure and ribbon type morphology of material. The performance of the single cell using purified carbon nanoribbon as the anode has been studied and the reversible lithium intercalation capacity has been found about 345 mAh/g, of which 335 mAh/g remain after 14th cycle. The columbic efficiency has been stabilized at approximately 98% from the 5th cycle.     

Effects of particle size and carbon coating on electrochemical properties of LiFePO4/C prepared by hydrothermal method

In this study, well-crystallized phase pure LiFePO₄/C (LFP/C) powders were synthesized using the hydrothermal reaction method. To improve the electronic conductivity of the LFP/C powder after ball-milling, the LFP/C powders were double-coated with carbon. Scanning electron microscopy and transmission electron microscopy were employed to observe the micromorphology of the samples and the carbon coating, which was analyzed using Raman spectroscopy. Furthermore, the electrochemical properties were evaluated using cyclic voltammetry, electrochemical impedance spectra, and the charge–discharge cycling test. The ball-mill and the process for double-coating carbon decrease the particle size and increase the conductivity of the LFP/C, thereby reducing the Li-ion diffusion length and improving the reversibility of the Li-ion intercalation/de-intercalation in the LFP/C crystallites. The capacity of the small-particle LFP/C with the double-layer carbon coating was 133 mAh/g at 0.1 °C, and remained at 83 mAh/g as the charge–discharge rate increased to 10 °C. In addition, good cycle stability was observed, with a retention rate of 98 % after 50 cycles at 1 °C.     

Hierarchical three-dimensional ZnCo₂O₄ nanowire arrays/carbon cloth anodes for a novel class of high-performance flexible lithium-ion batteries

Flexible electronics is an emerging and promising technology for next generation of optoelectronic devices. Herein, hierarchical three-dimensional ZnCo(2)O(4) nanowire arrays/carbon cloth composites were synthesized as high performance binder-free anodes for Li-ion battery with the features of high reversible capacity of 1300-1400 mAh g(-1) and excellent cycling ability even after 160 cycles with a capacity of 1200 mAh g(-1). Highly flexible full batteries were also fabricated, exhibiting high flexibility, excellent electrical stability, and superior electrochemical performances.     

Lithium Titanate Cuboid Arrays Grown on Carbon Fiber Cloth for High‐Rate Flexible Lithium‐Ion Batteries

High‐rate performance flexible lithium‐ion batteries are desirable for the realization of wearable electronics. The flexibility of the electrode in the battery is a key requirement for this technology. In the present work, spinel lithium titanate (Li₄Ti₅O₁₂, LTO) cuboid arrays are grown on flexible carbon fiber cloth (CFC) to fabricate a binder‐free composite electrode (LTO@CFC) for flexible lithium‐ion batteries. Experimental results show that the LTO@CFC electrode exhibits a remarkably high‐rate performance with a capacity of 105.8 mAh g^?1 at 50C and an excellent electrochemical stability against cycling (only 2.2% capacity loss after 1000 cycles at 10C). A flexible full cell fabricated with the LTO@CFC as the anode and LiNi_0.5Mn_1.5O₄ coated on Al foil as the cathode displays a reversible capacity of 109.1 mAh g^?1 at 10C, an excellent stability against cycling and a great mechanical stability against bending. The observed high‐rate performance of the LTO@CFC electrode is due to its unique corn‐like architecture with LTO cuboid arrays (corn kernels) grown on CFC (corn cob). This work presents a new approach to preparing LTO‐based composite electrodes with an architecture favorable for ion and electron transport for flexible energy storage devices.     

Co-coating effect of GdPO4 and carbon on LiFePO4 cathode surface for lithium ion batteries

The electronic conductivity enhanced has been extensively studied and reported in lithium iron phosph-ate (LiFePO₄). However, only few existing literatures are available for researchers to enhance simultaneously the ion and electronic conductivity of LiFePO₄. Herein, we disclose that the LiFePO₄ is co-coated with novel GdPO₄ and Carbon via a hydrothermal-assisted solid-phase method, contributing to particle size and dispersibility. What surprising is that the ionic and electronic conductivity of the material is significantly enhanced, and the interfacial side reaction is effectively inhibited between the materials and the electrolytes. The diverse proportions of the mixed coating (LiFePO₄/C&xGdPO₄ (x = 0, 1 wt%, 2 wt%, 3 wt%, 4 wt%)) are synthesized compared with bare LiFePO₄. The experimental results suggest that LiFePO₄/C&0.03GdPO₄ exhibits the most excellent electrochemical performance. There is discharge capacity of 158, 148.8, 141.6, 134.9, 121.8, 104.9, and 86.7mAh/g at 0.1, 0.2, 0.5, 1, 2, 5, and 10 C rates, respectively.     

Polyol process for the synthesis of LiFePO4 rhombohedral particles

As a new approach, LiFePO₄ nanoparticles were directly synthesized from precursors iron(III) nitrate and lithium dihydrogen phosphate by a polyol process without post heat treatment in one step. The obtained powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and combined thermogravimetry and differential scanning calorimetry and mass spectroscopy TG/DSC/MS. The X-ray diffraction showed the orthorhombic crystal structure of LiFePO₄ without any impurity phases. The synthesized LiFePO₄ has rhombohedral morphology with high aspect ratio with a thickness of less than 100 nm. TG/DSC/MS revealed a weight loss of only 10.9 wt.% when heating up to 1000 °C. Electrodes prepared from the LiFePO₄ particles were electrochemically characterized by cycling at 0.1C current rate and temperatures in half cell measurements against lithium foil between 2 and 4.2 V in an EC/DMC electrolyte with 1 M LiPF₆ as conductive salt. A reversible specific capacity of 146 mAh/g was achieved by applying carbon coating on the rhombohedral particles.     

Facile synthesis of carbon coated LiFePO4 nanocomposite with excellent electrochemical performance through in situ formed lithium stearate pyrolysis route

Carbon coated LiFePO₄ (LiFePO₄/C) nanocomposite is successfully synthesized at a comparatively low temperature (400 °C) via a pyrolysis process of in situ formed lithium stearate. The obtained products are characterized by X-ray diffraction, electron microscopy, thermogravimetry, infrared and X-ray photoelectron spectroscopy. Experimental results indicate that the in situ formed lithium stearate can decompose at ∼290 °C, which is beneficial for the formation of carbon coating and reduction of Fe³⁺ species, and then the crystallized LiFePO₄/C nanocomposite can be formed at 400 °C without other intermediate products. As cathode material of Li-ion battery, the obtained LiFePO₄/C nanocomposite exhibits a good rate and cycling performance with a high discharge capacity of ∼160 mAh g⁻¹ (>94% theoretical capacity of LiFePO₄) at a current density of 1 C (170 mA g⁻¹), and ∼96% of its initial capacity can be retained after 200 charging/discharging cycles. Even at a high current density (10 C), the LiFePO₄/C nanocomposite still presents a discharge capacity as high as ∼100 mAh g⁻¹. The excellent electrochemical performances of the present LiFePO₄/C nanocomposite mainly originate from the good crystallinity, small particles and enhanced electronic conductivity of the materials coated and linked by carbon layers.     

Recycling Bacteria for the Synthesis of LiMPO4 (M = Fe,Mn) Nanostructures for High‐Power Lithium Batteries

In this work, a novel waste‐to‐resource strategy to convert waste bacteria into a useful class of cathode materials, lithium metal phosphate (LiMPO₄; M = Fe, Mn), is presented. Escherichia coli (E. coli) bacteria used for removing phosphorus contamination from wastewater are harvested and used as precursors for the synthesis of LiMPO₄. After annealing, LiFePO₄ and LiMnPO₄ nanoparticles with dimensions around 20 nm are obtained. These particles are found to be enveloped in a carbon layer with a thickness around 3–5 nm, generated through the decomposition of the organic matter from the bacterial cell cytoplasm. The battery performance for the LiFePO₄ is evaluated. A high discharge capacity of 140 mAh g^?1 at 0.1 C with a flat plateau located at around 3.5 V is obtained. In addition, the synthesized particles display excellent stability and rate capabilities. Even under a high C rate of 10 C, a stable discharge capacity of 75.4 mAh g^?1 can still be achieved.     

锂离子电池正极材料LiM0.1Ni0.4Mn1.5O4(M:Co,Cr,Fe)纳米纤维的制备与电化学性能

利用高压静电纺丝技术与溶胶凝胶法相结合制备出了锂离子电池正极材料LiM_(0.1)Ni_(0.4)Mn_(1.5)O_4(M:Co,Cr,Fe)纳米纤维。采用X射线衍射(XRD)、场发射扫描电镜(FESEM)对材料的晶体结构和表面形貌进行了表征,并采用恒流充放电手段研究了材料在室温下的循环稳定性和倍率特性。结果表明:LiFe_(0.1)Ni_(0.4)Mn_(1.5)O_4材料以0.5C充放电循环100周后容量保持率高达95.5%,显示了良好的循环稳定性;而LiCr_(0.1)Ni_(0.4)Mn_(1.5)O_4材料以10C放电比容量仍高达120mAh/g,显示出了极好的倍率特性。