锂离子电池用Sn/C复合材料的碳热还原法制备

采用碳热还原法制备了Sn/C复合材料,通过XRD、SEM、恒流充放电循环、慢速扫描循环伏安(CV)等方法对材料以及其电化学嵌脱锂性能做了研究。结果表明：Sn球均匀分散在絮状碳材料中,加热时间越长,Sn球粒径越大。加热8 h得到材料的首次嵌锂比容量可达1 014 mAh·g^-1,循环15周以后的嵌锂比容量为406 mAh·g^-1。     

碳热还原原位合成锂离子电池硅/碳复合负极材料研究

以一氧化硅和蔗糖为原料,通过高能球磨和后续热解原位制备硅/碳复合材料。采用X射线衍射仪(XRD)和高分辨透射电子显微镜(HRTEM)对其进行了表征,得到的纳米(小于50 nm)硅颗粒均匀地分散于无定形碳基体中。复合材料电极电化学测试显示,循环50次其可逆容量仍保持在650 mAh·g-1以上,平均每次容量衰减率仅为0.27%。优异的电化学性能主要归因于原位生成的纳米硅颗粒处于无定形碳基体中对其体积变化具有良好的缓冲作用及纳米硅颗粒周围的石墨相对于导电性的改善。     

锂离子电池用硅/碳复合负极材料

以聚氯乙烯（PVC）、纳米硅粉和小粒径的人造石墨为前驱物,利用高温热解 反应,使纳米的硅和石墨微粒高度均匀地分散在PVC热解产生的碳中,形成一种新 型硅碳复合嵌锂材料,电化学测试表明：该复合材料首次充放电效率约为84%。可 逆比窝容量500mAh·g~（-1）左右,30次循环后容量维持在90%以上。另外,该复 合材料充放电平台经目前锂离子电池广泛采用的中间相碳微球（CMS）高0.15V左右 ,这有助于提高电池的充电倍率性能和操作安全性。     

碳在锂离子电池硅碳复合材料中的作用

随着低比容量硅碳复合材料(<500 mAh/g)在锂离子电池中的商业化应用,硅基负极材料也从实验室研究走向了产业化发展。近年来的研究工作中,许多方法被用来解决硅在循环过程中体积变化(>300%)所带来的一系列问题。在材料结构方面,从最初的硅材料纳米化、硅与其他材料复合等技术手段转变到了硅碳复合材料二次颗粒的结构设计、表面包覆层设计等方法;在应用性能方面,除了早期文献报道的材料比容量、循环性能等参数外,还增加了材料比表面积、振实密度、首次及循环库仑效率等更符合电池实际应用要求的性能参数研究,从而极大地推动了硅基负极材料的商业化应用进程。本文首先综述了近年来硅碳复合材料组成、结构设计的发展脉络,进一步分析了由石墨、软碳、硬碳、碳纤维和石墨烯等碳源合成的硅碳复合材料的结构特点,并对其电化学性能进行分析对比,总结了碳在硅碳复合材料结构及其性能上发挥的作用。最后,对硅碳复合材料制备过程中的结构设计要求和碳材料的选择进行了分析和展望。     

锂离子电池硅纳米粒子/碳复合材料

硅由于其超高的理论比容量有望取代石墨成为下一代锂离子电池负极材料,但是硅在充放电过程中巨大的体积膨胀(~300%)会导致材料粉化从集流体上脱落,同时不断形成固相电解质层,造成不可逆容量损失,而材料纳米化和碳复合是解决这些问题的有效手段。本文介绍了硅在循环过程中容量衰减机理,并综述了硅纳米粒子与碳材料复合的最新进展,主要包括包覆型、核壳型以及嵌入型硅碳负极材料,并对核壳型与嵌入型做了重点探究,最后对硅纳米粒子/碳复合材料存在的问题进行分析并展望其研究前景。     

镁热还原法制备有序介孔Si/C锂离子电池负极材料及其电化学性能

以SBA-15为前驱体,在660 ℃下通过镁热还原反应得到介孔硅材料,并对其进行碳包覆处理,成功地制备了有序介孔Si/C（OMP-Si/C）复合材料。该OMP-Si/C材料保留了SBA-15模板的有序蜂窝孔道,并且形成具有高堆积密度的莲藕链束结构。文中还提出了一个SBA-15镁热还原液态环境反应模型,探讨了660 ℃下硅的高度有序介孔与莲藕链束结构的形成机理。利用X射线衍射（XRD）仪、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、氮气吸脱附法及拉曼光谱对样品物相和微观形貌进行了表征。这种高度有序介孔Si/C复合材料具有优异的电化学性能,展现出其在第二代锂电池负极材料领域中的潜在应用价值。     

固相-碳热还原法制备高密度LiFePO4/C复合材料及其电化学性能

以无机Fe2O3和有机柠檬酸铁(FeC6H5O7·5H2O)两种价廉的三价铁化合物为铁源, 利用柠檬酸铁中的柠檬酸根为碳源和还原剂, 通过固相-碳热还原法成功制备了高密度LiFePO4/C复合材料. 采用热重与差示扫描量热法研究了反应历程, 并利用X射线衍射、扫描电镜、激光粒度分布仪、振实密度测试仪和恒流充放电技术对材料的微观结构和物理化学性能进行了表征. 研究结果表明, 在700 ℃下焙烧制备的材料结晶良好、粒径大小适中, 具有优良的电化学性能和较高的振实密度. 该材料在17 mA·g-1电流密度下充放电可以得到129 mAh·g-1的首次放电比容量, 20周循环后比容量基本无衰减. 其晶粒由纳米颗粒和微米颗粒组成, 呈多峰的粒径分布, 振实密度达1.41 g·cm-3.     

锂离子电池正极材料LiFePO4/ C的合成研究

以三价铁化合物作为铁源，采用碳热还原法一步合成得到锂离子电池正极材料LiFePO₄。利用X射线衍射仪、扫描电镜、碳硫分析法和电化学性能测试方法对磷酸铁锂材料的物相结构、表面形貌、含碳量(质量分数)以及电性能进行分析研究。讨论了烧结温度、烧结时间和掺碳量对材料电性能的影响。结果表明，LiFePO₄的电性能与烧结温度、时间以及掺碳量有密切的关系，在优化试验条件下制备的正极材料LiFePO₄，以电流密度为17 mA·g^-1充放电，首次放电容量达到141.8 mAh·g^-1，80次循环后放电容量为137.7 mAh·g^-1，容量保持率为97.1%。     

废旧锂离子电池基石墨烯/聚苯胺复合材料制备及其电化学性能研究

以废旧手机锂离子电池回收的负极石墨粉制备的氧化石墨烯(GO)和苯胺单体为原料,利用GO活化H_2O_2产生的·OH为氧化剂,采用原位复合法制备了不同质量比的石墨烯/聚苯胺复合材料,通过FTIR、XRD和SEM对其进行了表征,并利用循环伏安、交流阻抗、恒电流充放电等对其电化学性能进行测试。结果表明,该类石墨烯/聚苯胺复合材料具有良好的电化学性能,当电流密度为100mA/g时,质量比为1∶10制备的石墨烯/聚苯胺复合材料(rGO/PANI-10)的比电容达到481F/g,较石墨烯比容量(161F/g)提高了199%,较聚苯胺比容量(351F/g)提高了37%;在500mA/g电流密度下,rGO/PANI-10充放电循环1000圈后,电容保持率为77%,表现出较好的循环稳定性。     

锂离子电池Sn30Co30C40三元合金负极材料的制备与性能研究

随着人们对高比能量锂离子电池需求的逐步增加,Sn基合金成为目前高比容量负极材料的研究热点.以低成本的金属氧化物、活性炭为原料经碳热还原法首先合成出中间产物CoSn2,再将Co、石墨引入,经高能球磨制备了Sn30Co30C40三元合金负极材料.材料呈现微米级颗粒形貌,其内部是由均匀分散于无定形碳中10 nm左右CoSn晶粒所组成.材料的比容量为550 mAh/g左右,首次效率为80%左右,循环稳定性好、倍率性能优越,是一种非常有发展前景的高比容量锂离子电池负极材料.     

锂离子电池中的热效应

锂离子电池中的热效应;锂离子电池;电池材料;热分解;C80微量量热仪     

Design Strategies of Si/C Composite Anode for Lithium-Ion Batteries

Silicon-based materials that have higher theoretical specific capacity than other conventional anodes, such as carbon materials, Li₂TiO₃ materials and Sn-based materials, become a hot topic in research of lithium-ion battery (LIB). However, the low conductivity and large volume expansion of silicon-based materials hinders the commercialization of silicon-based materials. Until recent years, these issues are alleviated by the combination of carbon-based materials. In this review, the preparation of Si/C materials by different synthetic methods in the past decade is reviewed along with their respective advantages and disadvantages. In addition, Si/C materials formed by silicon and different carbon-based materials is summarized, where the influences of carbons on the electrochemical performance of silicon are emphasized. Lastly, future research direction in the material design and optimization of Si/C materials is proposed to fill the current gap in the development of efficient Si/C anode for LIBs.     

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.     

Simplified Synthesis of Biomass-Derived Si/C Composites as Stable Anode Materials for Lithium-Ion Batteries

Synthesis of silicon/carbon (Si/C) composites from biomass resources could enable the effective utilization of agricultural products in the battery industry with economical as well as environmental benefits. Herein, a simplified process was developed to synthesize Si/C from biomass, by using a low-cost agricultural byproduct “rice husk (RH)” as a model. This process includes the calcination of RH for SiO₂/C and the reduction of SiO₂/C by Al in molten salts at a moderate temperature. This process does not need the removal of carbon before thermal reduction of SiO₂, which is thought to be necessary to avoid the formation of SiC at elevated temperatures. Thus, carbon derived from biomass can be directly used for Si/C composites for anode materials. The resultant Si/C shows a high reversible capacity of 1309 mAh g⁻¹ and long cycle life (300 cycles). This research advocates a new and simplified strategy for the synthesis of RH-based biomass-derived Si/C, which is beneficial for low-cost, environmentally friendly, and green energy storage applications.     

Nanostructure Sn/C Composite High-Performance Negative Electrode for Lithium Storage

Tin-based nanocomposite materials embedded in carbon frameworks can be used as effective negative electrode materials for lithium-ion batteries (LIBs), owing to their high theoretical capacities with stable cycle performance. In this work, a low-cost and productive facile hydrothermal method was employed for the preparation of a Sn/C nanocomposite, in which Sn particles (sized in nanometers) were uniformly dispersed in the conductive carbon matrix. The as-prepared Sn/C nanocomposite displayed a considerable reversible capacity of 877 mAhg⁻¹ at 0.1 Ag⁻¹ with a high first cycle charge/discharge coulombic efficiency of about 77%, and showed 668 mAh/g even at a relatively high current density of 0.5 Ag⁻¹ after 100 cycles. Furthermore, excellent rate capability performance was achieved for 806, 697, 630, 516, and 354 mAhg⁻¹ at current densities 0.1, 0.25, 0.5, 0.75, and 1 Ag⁻¹, respectively. This outstanding and significantly improved electrochemical performance is attributed to the good distribution of Sn nanoparticles in the carbon framework, which helped to produce Sn/C nanocomposite next-generation negative electrodes for lithium-ion storage.     

Sol-gel Synthesis and Electrochemical Performance of Li4-xMgxTi5-xZrxO12 Anode Material for Lithium-ion Batteries

The anode materials Li_4?xMg_xTi_5?xZr_xO₁₂ (x=0, 0.05, 0.1) were successfully synthesized by sol‐gel method using Ti(OC₄H₉)₄, CH₃COOLi·2H₂O, MgCl₂·6H₂O and Zr(NO₃)₃·6H₂O as raw materials. The crystalline structure, morphology and electrochemical properties of the as‐prepared materials were characterized by XRD, SEM, cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS) and charge‐discharge cycling tests. The results show that the lattice parameters of the Mg‐Zr doped samples are slightly larger than that of the pure Li₄Ti₅O₁₂, and Mg‐Zr doping does not change the basic Li₄Ti₅O₁₂ structure. The rate capability of Li_4?xMg_xTi_5?xZr_xO₁₂ (x=0.05, 0.1) electrodes is significantly improved due to the expansile Li⁺ diffusion channel and reduced charge transfer resistance. In this study, Li_3.95Mg_0.05Ti_4.95Zr_0.05O₁₂ represented a relatively good rate capability and cycling stability, after 400 cycles at 10 C, the discharge capacity retained as 134.74 mAh·g^?1 with capacity retention close to 100%. The excellent rate capability and good cycling performance make Li_3.95Mg_0.05Ti_4.95Zr_0.05O₁₂ a promising anode material in lithium‐ion batteries.     

锂离子电池非水电解质中Li迁移特性

电解质是锂离子电池的重要组成部分之一，其中Li＋的迁移特性对电池性能具有显著影响。本文综述了用于锂离子电池的凝胶、聚合物和非水液态电解质中Li+迁移特性的研究进展，分析了影响Li＋迁移的主要因素，并提出了进一步的研究重点和新的研究方法。