二元共聚物热解碳包覆的石墨负极材料

以苯萘二元共聚物包覆天然石墨后进行热处理，用所制备的包覆石墨作为锂离子电池的负极材料，与包覆前石墨材料相比较，可逆容量提高了10％，不可逆容量降低了7％，循环性能也得到了大的改善. X射线分析表明，改性后该石墨晶体中三方石墨的含量增高.     

硅/石墨复合物用作锂离子电池负极材料

以石墨和纳米硅粉为原料, 利用机械球磨的方法制备了硅/石墨复合物, 用作锂离子电池负极材料. 采用XRD, SEM以及电化学测试等手段对材料进行了结构表征和性能测试. 通过球磨不同质量比的硅和石墨, 并对相应的复合物进行充放电测试, 寻找到了硅和石墨的最佳比例, 其值为1∶9. 实验结果表明, 所得材料既具备高于纯纳米硅的循环性能, 又具有比石墨高的可逆容量.     

改性石墨用于锂离子电池负极

石墨可用于锂离子电池负极材料，其改性方面的研究主要有：石墨的还原、氧化、表面包膜以及物理法处理。这些方法可以改变石墨的电子状态及表面结构，能够提高石墨的性能。本文介绍了改性石墨用于锂离子电池负极的研究概况。     

Preparation of Anode Material for Lithium Ion Battery by Chemical Oxidation

Sincetheoilcrisisinthe60'sand70's,ithasbeenrealizedthatthenaturalresourcesareveryimportantandtheresearchoflithiumsecondarybatterywasthenbegun.Recently,theurgentdemandofmicroelectronicsforsecondarybatterywithhighenergydensityandlightweighthasgreatlystimulatedthedevelopmentoflithiumsecondarybattery.Onlyintheearly90's,didthiskindofbatterybecomecommercialwhenitwasfoundthatgraphitecansubstitUtelithiumorlithiumalloysandsolvetheproblemsofsafetyandcyclelife.However,thesynthesisconditionforgraphiteiscr…     

锂离子在石墨负极材料中扩散系数的测定

锂离子电池是以各种碳材料为负极而起来的一 种新型电池,成功地解决了以 为负极瓣锂可充电电池的安全性问题,已经应用于锂离子电池的负极材料有石墨和石油焦炭,正在研究的负极材料有热解碳,石墨化碳纤维,硼炭或硼炭氮化合物以及锡基氧化物等[1],石墨的比容量要比石油焦炭的比容量高一倍左右,其理论比容量372mA.h.g^-1,但锂离子在石墨材料中的扩散系数比较低,限制了以其为负极材料的电池的大电流充放电能力,锂离子在电极材料中的扩散系数可以用多种电化学方法测量得到,主要有：电位间歇滴定方法（PITT）（Potentiostatic Intermittent Titratiobn Technique)^[2,3,4,6],恒电流间歇滴定法（GITT）（Galvanostatic Intermittent Titration Technology)^[6],电流脉冲松弛法（CPR）（Current Pulse Relaxation Method)^[3,6]和交流阻抗法（A－C Technology)^[4,5,6],GITT,CPR,A-C等方法测定锂离子扩散系数时,由于相变发生处dE/dy值不容易准确得到（相变时,dE/dy→0）,此时测得的扩散系数误差比较大,PITT方法测定锂离子扩展系统,不存在这个问题,能比较准确地测定整个嵌入组成范围内的锂离子扩散系数。     

A New Tin Graphite Intercalation Compound for Lithium Ion Batteries

IntroductionLithium ion batteries have attracted a great interestbecause of their commercial applications in portable de-vices[1,2].Great efforts have been made to improve theenergy density of new anode materials.For example,Sn-based compounds,such as SnO…     

纳米Sn-Co/石墨复合材料的制备、结构和电化学性能

以化学沉积法制备Sn-Co合金纳米粒子/石墨复合材料,XRD和Ram an光谱表征物相结构,SEM观察表面形貌.结果显示,500℃高温热处理的Sn-Co/石墨复合材料,其颗粒密集均匀地分散于石墨载体上.Sn-Co合金纳米粒子颗粒直径100 nm左右.Sn-Co/石墨电极具有较高的比容量和循环寿命,这可能是该合金纳米粒子与棒状石墨间的亲合能有效地阻止Sn的脱落,Sn-Co的颗粒间隙缓冲锂嵌脱过程的结构张力,防止合金的膨胀与粉化.     

酚醛树脂包覆氧化天然石墨作为锂离子电池负极材料

天然石墨经过浓硫酸氧化处理,酚醛树脂包覆并高温碳化后形成具有核壳结构的碳包覆氧化天然石墨复合材料.采用扫描电子显微镜(SEM),透射电子显微镜(TEM),X射线衍射(XRD),激光显微拉曼光谱(Raman)等检测技术对氧化处理以及酚醛树脂热解碳包覆前后天然石墨材料的结构与形貌进行分析与表征.结果表明,氧化处理与适量的酚醛树脂热解碳包覆有效修复了天然石墨表面的一些缺陷结构,使其表面更为光滑.电化学测试结果显示,经过氧化处理与酚醛树脂热解碳包覆后天然石墨材料电化学性能得到明显提高.酚醛树脂包覆量为9%时,复合材料表现出最好的电化学性能,其首次放电比容量为434.0mAh·g-1,40次循环后,放电比容量保持在361.6mAh·g-1,而未经处理的天然石墨放电比容量仅为332.3mAh·g-1.该改性方法有效提高了天然石墨材料的比容量,对其进一步应用具有重要意义.     

Integration of Graphite and Silicon Anodes for the Commercialization of High‐Energy Lithium‐Ion Batteries

Silicon is considered a most promising anode material for overcoming the theoretical capacity limit of carbonaceous anodes. The use of nanomethods has led to significant progress being made with Si anodes to address the severe volume change during (de)lithiation. However, less progress has been made in the practical application of Si anodes in commercial lithium‐ion batteries (LIBs). The drastic increase in the energy demands of diverse industries has led to the co‐utilization of Si and graphite resurfacing as a commercially viable method for realizing high energy. Herein, we highlight the necessity for the co‐utilization of graphite and Si for commercialization and discuss the development of graphite/Si anodes. Representative Si anodes used in graphite‐blended electrodes are covered and a variety of strategies for building graphite/Si composites are organized according to their synthetic methods. The criteria for the co‐utilization of graphite and Si are systematically presented. Finally, we provide suggestions for the commercialization of graphite/Si combinations.     

Graphite Anode for a Potassium‐Ion Battery with Unprecedented Performance

Graphite as an anode for the potassium ion battery (PIBs) has the merits of low cost and potentially high energy density, while suffering from limited cycle time and inferior stability. Herein we, using a concentrated electrolyte, demonstrate that formation of a robust inorganic‐rich passivation layer on the graphite anode could resolve these problems. Consequently, the PIBs with graphite anode could operate for over 2000 cycles (running time of over 17 months) with negligible capacity decay, and had a high area capacity over 7.36 mAh cm^?2 with a high mass loading of 28.56 mg cm^?2. These unprecedented performances of graphite are comparable to that of traditional lithium‐ion batteries, and may promote the rapidly development of high performance PIBs.     

Detection of Copper Deposition on Anodes of Over-Discharged Lithium Ion Cells by GD-OES Depth Profiling

A method based on glow discharge optical emission spectroscopy (GD-OES) depth profiling is developed to detect copper deposition on graphite electrodes for the first time. Commercial 18650 cells with graphite anodes were subject to Cu dissolution by over-discharge to 0 V. On a first approach, the depth profiles for Cu show significant differences for over-discharged cells compared to a baseline graphite electrode from cells discharged to the end-of-discharge voltage. An accumulation of Cu is found on the anode surface by GD-OES, which is consistent with SEM and EDX. The trend of the total Cu amount is compared with ICP-OES measurements.     

热处理温度对石墨复合负极材料电化学性能的影响

以球形天然石墨为原料,柠檬酸为碳源,通过喷雾造粒及高温热处理得到了高容量石墨复合(G/C)负极材料.利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和高分辨率透射电子显微镜(HRTEM)对样品物相和微观形貌进行表征,并通过恒流充放电及循环伏安(CV)研究了不同热处理温度对G/C材料电化学性能的影响.2 900 ℃制得样品既具有石墨负极电压曲线特性,又可释放出远高于商品化石墨负极的比容量:首次循环活化后充电比容量为423 mAh·g^-1,100次循环后仍高达416 mAh·g^-1,容量保持率为98%.     

热处理温度对石墨复合负极材料电化学性能的影响

以球形天然石墨为原料,柠檬酸为碳源,通过喷雾造粒及高温热处理得到了高容量石墨复合(G/C)负极材料。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和高分辨率透射电子显微镜(HRTEM)对样品物相和微观形貌进行表征,并通过恒流充放电及循环伏安(CV)研究了不同热处理温度对G/C材料电化学性能的影响。2900℃制得样品既具有石墨负极电压曲线特性,又可释放出远高于商品化石墨负极的比容量:首次循环活化后充电比容量为423mAh·g^-1,100次循环后仍高达416mAh·g^-1,容量保持率为98%。     

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。     

锂离子固相扩散控制下的材料放电过程

从理论上分析了在锂离子相扩散控制条件下,电极材料的恒流放电过程,数值计算的结果表明,Q值（放电时率和扩散时间常数之比）对材料的放电容量有非常重要的影响,模拟了LiMn2O4正极材料和石墨负极材料的恒流放电曲线,分析了颗粒粒径对这两种材料放电容量的影响。     

The Use of Graphitic Carbon Nitride Based Composite Anodes for Lithium‐Ion Battery Applications

Graphitic carbon nitride (gCN) is shown to undergo lithium insertion reactions applicable with lithium‐ion battery anodes. Lithium capacity was found to be substantially lower than theoretically expected, so the properties of gCN composited with conducting graphite (CG), which was added to improve the performance, were investigated. The electrodes exhibited a systematic increase in lithium uptake with CG content, but the capacity never exceeded that of graphite. It is shown that electron transport via conducting pathways was limiting. Li⁺ uptake for 10 % gCN was similar to a graphite electrode, indicating that gCN does play a role in determining the storage capacity.     

Ion Recognition and Analytical Application of a Fibroin Modified Electrode

A novel fibroin modified electrode with ion recognition was reported. The membrane with isoelectric point of pH 4.5, was modified on graphite and carbon fiber electrodes. The pH-responsive ion recognition of the modified electrode was investigated by use of some neurocompounds. The fibroin carbon fiber electrode has been used for in-vivo determination.     

Understanding High‐Rate K+‐Solvent Co‐Intercalation in Natural Graphite for Potassium‐Ion Batteries

Graphite shows great potential as an anode material for rechargeable metal‐ion batteries because of its high abundance and low cost. However, the electrochemical performance of graphite anode materials for rechargeable potassium‐ion batteries needs to be further improved. Reported herein is a natural graphite with superior rate performance and cycling stability obtained through a unique K⁺‐solvent co‐intercalation mechanism in a 1 m KCF₃SO₃ diethylene glycol dimethyl ether electrolyte. The co‐intercalation mechanism was demonstrated by ex situ Fourier transform infrared spectroscopy and in situ X‐ray diffraction. Moreover, the structure of the [K‐solvent]⁺ complexes intercalated with the graphite and the conditions for reversible K⁺‐solvent co‐intercalation into graphite are proposed based on the experimental results and first‐principles calculations. This work provides important insights into the design of natural graphite for high‐performance rechargeable potassium‐ion batteries.     

新型成膜电解液添加剂亚硫酸丁烯酯的电化学行为

合成制备了一种新的环状亚硫酸酯类有机溶剂——亚硫酸丁烯酯(BS). 量子化学计算结果表明, 亚硫酸丁烯酯有机溶剂分子的总能、LUMO值比碳酸丙烯酯有机溶剂的低, 具有较强的得电子能力, 不易被氧化. 其作为添加剂与碳酸丙烯酯(PC)混合应用于锂离子电池中, 可有效地抑制PC在石墨电极中的共插入, 能显著改善循环性能.     

四丁基六氟磷酸铵作为锂离子电池阻燃添加剂的研究

近年来关于锂离子电池造成的安全问题甚至事故的报道屡见不鲜,锂离子电池的安全问题已经成为人们关注的焦点. 我们用四丁基六氟磷酸铵（TBAPF₆）作为锂离子电池电解液阻燃添加剂,研究发现添加了TBAPF₆的电解液具有明显的阻燃效果,同时电解液电导率下降并不明显. LiCoO₂/Graphite全电池在添加了TBAPF₆的电解液中可逆容量会略有降低,但具有更优异的循环稳定性. 主要是由于TBAPF₆添加量的增加会影响石墨电极的库伦效率,延长活化时间. 通过对LiCoO₂/Graphite全电池绝热加速量热仪（ARC）测试,表明添加TBAPF₆对电池的燃烧有明显的抑制作用. 在TBAPF₆添加量至5%时,电池在300 ^oC内自放热速率不超过0.1^oC/min,电池的安全性显著提高.