纳米银复合的多孔生物质硅材料的制备及储锂性能EI北大核心CSCD

以废弃的谷壳为原料,通过镁热还原-银镜反应法成功制备了多孔硅/银复合纳米材料,并研究其结构形貌及储锂性能。结果表明:采用谷壳为原料获得的硅/银复合材料为纳米多孔结构,其粒径约为10~20 nm,纳米银的原位复合可显著提高电极的循环稳定性能、倍率性能和比容量。原位纳米银粒子复合后的Si/Ag电极50次循环后的容量依然能维持750.4 mA·h/g,为石墨类碳材料容量的2倍以上,较生物质硅电极提高了370.2 mA·h/g,采用800 mA/g的电流密度进行大电流充放电时,Si/Ag电极表现出618.3 mA·h/g的可逆容量,远高于Si电极380.2 mA·h/g的容量。性能的改善缘于复合后本体材料较高的导电性和电极/电解液界面的优良性能。     

纳米银复合的多孔生物质硅材料的制备及储锂性能

以废弃的谷壳为原料,通过镁热还原-银镜反应法成功制备了多孔硅/银复合纳米材料,并研究其结构形貌及储锂性能。结果表明:采用谷壳为原料获得的硅/银复合材料为纳米多孔结构,其粒径约为10～20 nm,纳米银的原位复合可显著提高电极的循环稳定性能、倍率性能和比容量。原位纳米银粒子复合后的Si/Ag电极50次循环后的容量依然能维持750.4 mA·h/g,为石墨类碳材料容量的2倍以上,较生物质硅电极提高了370.2 mA·h/g,采用800 mA/g的电流密度进行大电流充放电时,Si/Ag电极表现出618.3 mA·h/g的可逆容量,远高于Si电极380.2 mA·h/g的容量。性能的改善缘于复合后本体材料较高的导电性和电极/电解液界面的优良性能。     

高性能硅基复合锂离子电池负极制备及电化学性能EI北大核心CSCD

因硅具有高达4200 mA·h/g的理论嵌锂容量,成为目前最具有发展前景的锂离子电池负极材料。但是,因硅材料在嵌脱锂过程中存在巨大的体积膨胀(≥300%),制约了其作为锂离子电池负极的商业化应用。通过采用静电纺丝技术和碳源前驱体包覆相结合的方法,经过碳化处理制备的C@Si/C硅基复合负极。使用X射线衍射仪、扫描电子显微镜对材料的物相结构和微观形貌进行了表征,采用热重分析实验研究了聚乙烯吡咯烷酮包覆后所得材料质量随温度的变化情况,通过Raman测试考察了碳化后所得硅基负极材料的石墨化程度。对所制备的硅基负极材料进行了恒电流充放电、循环伏安及交流阻抗谱分析。结果表明:经碳包覆后的静电纺丝Si/C纤维相较于未包覆前,电化学性能有了明显提升。在0.1 A/g的电流密度下,首次放电容量可达到1401.4 mA·h/g,首次Coulombic效率高达70.22%,经100圈循环后容量仍保持在582.6 mA·h/g,倍率测试结果表明,经过1.0 A/g的大电流密度测试后,在0.1 A/g的电流密度下,仍具有622.2 mA·h/g的可逆容量。     

二硫化钼复合导电碳作为高性能钠离子电池负极材料的研究

通过水热法制备出导电碳负载的二硫化钼纳米片（MoS2@C），显著改善了二硫化钼循环稳定性和倍率性能：在0.1 A/g电流密度下，循环100次后，可逆比容量依然高达466.3 mA·h/g，容量保持率达90.6%；在10 A/g的电流密度下，可逆比容量高达321.5 mA·h/g；在1A/g电流密度下长循环500次后，可逆比容量为313 mA·h/g，未发生衰减。这是因为二硫化钼以导电碳作为基底后，既可以提高电子和钠离子在复合材料中的扩散效率，又可以抑制二硫化钼的团聚，另外，小尺寸的二硫化钼可以缩短钠离子的传递路径，之间的空隙为二硫化钼体积的膨胀提供了空间。通过对两个电极的动力学分析，发现钠离子在MoS2@C内部具有更高的扩散效率，赝电容控制行为是MoS2@C电极具有优异倍率性能的主要原因。     

复合溶胶–凝胶一锅法制备锂离子电池氧化亚硅/碳复合负极材料

采用复合溶胶–凝胶法结合后续热处理,制备了具有包埋结构的氧化亚硅/碳(SiO_x/C)复合负极材料。扫描电子显微镜分析结果表明:氧化亚硅纳米颗粒嵌入在无定形碳中。电化学性能测试表明:SiO_x/C复合材料具有较高的比容量、优异的循环稳定性和倍率性能。材料在0.1 A/g的电流密度下100次循环后的可逆比容量为710 m A·h/g,容量几乎无衰减;在1.6 A/g的电流密度下,可逆比容量为380 m A·h/g。优异的电化学性能是由于材料的包埋结构能有效地缓冲SiO_x充放电过程中的体积膨胀,保证材料的结构完整性和电化学循环稳定性。     

基于表面改性纳米硅复合负极材料的制备及其性能EI北大核心CSCD

基于简单易操作的湿法包覆制备了以纳米硅粉体和石墨(G)为主要原料,添加表面活性剂脂肪醇聚氧乙烯醚和石墨烯(GR)的Si/C@GR/G复合材料。研究了不同组分配比对复合材料的成分、形貌及电化学性能的影响。结果表明:制得的复合材料具有良好的循环稳定性,体积膨胀得到缓解。当复合材料中硅质量分数为10%,首次放电比容量约为730 mA·h/g,在电流密度为100 mA/g经100次循环后,其放电比容量稳定维持在500 mA·h/g左右,也展现了良好的倍率性能,首次Coulombic效率达到87.27%,相比纯硅不足70%的效率有了大幅度提高。     

聚苯胺包覆对提高单质硫正极材料的性能研究

采用原位聚合法合成了聚苯胺包覆硫复合材料,并分析了产品的晶体结构和表面形貌。苯胺的聚合倾向于在单质硫颗粒表面进行,形成聚苯胺包覆的硫复合材料。以0.2 mA/cm2电流密度充放电,含聚苯胺为15%的聚苯胺/硫复合材料的首次放电容量为1 134.01 mA.h/g,比未改性硫电极增加了82.42%;充放电循环30次后放电电容量为526.89 mA.h/g。当充放电电流密度提高到0.30、.4 mA/cm2时,聚苯胺/硫复合材料的放电容量分别为704.81、194.77 mA.h/g。改性后的聚苯胺/硫复合材料的电化学性能得到了较大的改善。     

柔性、自支撑CNT/Si复合薄膜的制备及储能性能

开发了一种制备大面积CNT/Si柔性自支撑薄膜的方法,制备的CNT/Si复合薄膜尺寸可调且具有良好的柔性。作为锂离子电池负极,薄膜中硅的负载量对电极比容量及循环稳定性有显著影响。硅负载量为52%的CNT/Si复合电极表现出优良的电化学性能,1 A/g电流密度下电极充电比容量为1156 mA·h/g,循环200圈可逆充电比容量为975 mA·h/g,容量保持率达84%。     

石墨烯/SnO2/Si@PPy复合材料的制备及电化学性能

以氧化石墨烯和Sn Cl2为原料,通过微波水热法合成了石墨烯/SnO_2复合材料(GS),以过硫酸铵为引发剂,通过吡咯在Si粉表面原位氧化聚合制备了Si@PPy(SP)包覆结构,最后通过微波水热组装法制备了石墨烯/SnO_2/Si@PPy复合材料(GSSP)。采用SEM、TEM、XRD、Raman和BET对GS、SP和GSSP材料的形貌和结构进行表征,并以GSSP复合材料为负极组装半电池进行倍率、循环、CV和EIS等电化学性能测试。结果表明,GSSP复合材料具有优异的倍率性能,在100 mA/g电流密度下,放电和充电的平均比容量分别为948.44和869.63 mA·h/g。1000 mA/g电流密度下,经过400次循环放电和充电的比容量保持率高达90.69%和89.34%。     

镁热还原法制备多孔硅碳复合负极材料

分别以介孔二氧化硅(SBA-15和 MCM-48)和硅藻土为硅源,通过镁热还原制备多孔硅,然后向多孔硅中注入有机碳前躯体,经过高温碳化处理得到多孔Si/C复合负极材料。采用X射线衍射仪、Raman光谱仪、场发射扫描电子显微镜和N2吸附脱附测试仪对合成的材料分别进行了表征,研究了多孔 Si/C 复合材料的电化学性能。结果表明：镁热还原介孔二氧化硅可以得到多孔硅材料,碳加入到多孔硅材料中可以有效提高材料的电子电导率,可明显改善材料的循环稳定性。同时多孔结构可以有效缓解硅基材料充放电过程中的体积应力,提高材料的循环稳定性。以SBA-15、MCM-48和硅藻土为硅源制备得到的3种多孔Si/C复合材料在200 mA/g电流密度下循环30次之后的可逆容量分别为712、664、463 mA·h/g。     

石墨烯负载纳米二硫化钴的制备及其在锂离子电池方面的应用研究

采用二次水热法将纳米二硫化钴负载于石墨烯上,并通过结构表征和电化学性能测试,探讨了纳米二硫化钴/石墨烯材料作为锂离子电池负极的性能。电容量测试结果表明：在电流密度为100 mA/g条件下,二硫化钴/石墨烯复合材料的首周充放电容量分别为1 610 mA·h/g和774 mA·h/g,测算出的库伦效率为48.1%;循环性能测试结果表明：经过50次循环测算后的复合材料的放电比容量为302 mA·h/g,容量保持率为33.4%;倍率性能测试结果表明：当电流密度回复到100 mA/g时,复合材料的比容量恢复至550 mA·h/g。实验制备的纳米二硫化钴/石墨烯复合材料在锂电池负极的应用上表现出了优异的循环性能和倍率性能。     

Sandwich structure of carbon-coated silicon/carbon nanofiber anodes for lithium-ion batteries

For electrospun silicon/carbon nanofiber composites, the surface precipitation of silicon nanoparticles can cause poor cycle stability. To solve this, a carbon-coated silicon/carbon nanofiber (Si/C@C) composite with a ‘sandwich’ structure is constructed by hydrothermal reaction of glucose and an electrospun silicon/carbon nanofiber, followed by high-temperature carbonization. The effects of the thickness of the carbon coating layer and calcining temperature on the electrochemical performance are studied. The results showed that carbon is uniformly and continuously coated on the surface of the composite fibers, which avoid direct exposure of precipitated silicon on the surface of the nanofibers to the electrolyte, reduce the occurrence of side reactions and is conducive to the stable formation of SEI films. At the same time, the carbon shell inhibit the volume expansion of silicon to a certain extent and improve the conductivity of the composites. Consequently, the obtained Si/C@C exhibit good rate performance and cycle stability. With the optimised carbon coating thickness and calcination temperature, the obtained electrodes deliver a reversible capacity of 1120 and 683 mA h g^-1 at a current density of 0.1 and 2 A g^-1 respectively, and a specific capacity of 602 mAh∙g^-1 at a current density of 1 A g^-1 after 100 cycles, a capacity retention rate of 80%. The facilely synthesised Si/C@C composite shows potential applications in high-capacity silicon-based anode materials.     

Preparation of graphene supported porous Si@C ternary composites and their electrochemical performance as high capacity anode materials for Li-ion batteries

Graphene supported porous Si@C ternary composites had been synthesized by various routes and their structural, morphological and electrochemical properties were investigated. Porous Si spheres coated with carbon layer and supported by graphene have been designed to form a 3D carbon conductive network. Used as anode materials for lithium ion batteries, graphene supported porous Si@C ternary composites demonstrate excellent electrochemical performance and cycling stability. The first discharge capacity is 2184.7 mA h/g at a high current density of 300 mA/g. After 50 cycles, the reversible capacity is 652.4 mA h/g at a current density of 300 mA/g and the coulomb efficiency reaches at 98.7%. Due to their excellent electrochemical properties, graphene supported porous Si@C ternary composites can be a kind of promising anode materials for lithium ion batteries.     

Nano-porous Si/C composites for anode material of lithium-ion batteries

Nano-porous silicon composite incorporated with graphite and pyrolyzed carbon was synthesized and investigated as a promising anode material for lithium-ion batteries. The nano-porous Si/graphite composite was prepared via two-step ball-milling followed by etching process. Then carbon was incorporated by using different approaches. The nano-porous Si/graphite/C composite exhibits a reversible capacity of about 700 mAh/g with no capacity loss up to the 120th cycle at a constant current density of 0.2 mA/cm². The superior electrochemical characteristics are attributed to the nanosized pores in Si particles, which suppress the volume effect, and buffering action as well as excellent electronic and ionic conductivity of carbon materials.     

柔性自支撑PDDA-Si/G纳米复合薄膜的制备及储锂性能

通过静电自组装技术成功制备得到柔性自支撑聚二烯二甲基氯化铵-Si/石墨烯(PDDA-Si/G)纳米复合薄膜。该复合薄膜无添加黏结剂及导电炭黑且仍能保持电极结构的完整性,其中石墨烯提供完整的导电网络和机械韧性。电化学测试结果表明,当电流密度为0.2 A/g,复合材料的比容量可达1439.9 (mA·h)/g,库仑效率保持98%以上。且在高电流密度(2 A/g)下,复合材料的比容量仍可维持在499.9 (mA·h)/g,远高于商品化纯Si电极的电化学性能。     

吸附电活性染料的活性炭电极电化学性能

采用商用活性炭（AC）吸附二元混合染料亚甲基蓝（MB）和胭脂红（AR18）,制备得到AC/(MB+AR18)电极材料。比较单一活性炭（AC）和吸附不同浓度的二元混合染料后的活性炭[AC/(MB+AR18)]的电化学性能。三电极体系的测试结果表明：在1mol/L H₂SO₄电解液中,当电流密度为1A/g时,吸附了浓度为400mg/L污染物的AC/(MB+AR18)比电容为182F/g,高于单一AC的比电容（109F/g）。随后选用性能最优的AC/(MB+AR18)-400作为电极材料,组装对称超级电容器器件,发现工作电压窗口从只用AC组装的对称超级电容器的1.1V提高到1.5V,电流密度为0.75A/g时,功率密度为843.84W/kg,能量密度可达32.23W·h/kg,远远高于AC组装的超级电容器(4.74W·h/kg),说明MB和AR18不仅为AC提供额外的法拉第电容,同时有助于提高其工作电压窗口。     

Si/VGCF复合材料的储锂性能

以纳米硅颗粒为原料,采用液相法制备了硅纳米粒子与气相生长碳纤维(VGCF)复合的材料(Si/VGCF)。考察了Si/VGCF制备工艺和VGCF的最佳含量,分别采用SEM和TEM表征了Si/VGCF材料形貌和晶体结构,测试和计算了材料电导、BET比表面积和孔尺寸数据。采用循环伏安、恒流充放电和交流阻抗等测试了Si/VGCF复合电极的电化学性能,并与其他碳材料进行了对比分析。结果表明,Si与VGCF形成了多级框架结构,丰富了离子和电子传输网络;同时发达的孔结构也缓解了Si粒子在嵌/脱锂过程中的体积效应,使电极活性材料的利用率和电化学稳定性显著提高。当m(Si)∶m(VGCF)为1:0.5时,Si/VGCF复合电极在500 mA/g的电流密度下,充放电循环100次后,可逆容量高达1470 mA·h/g。     

Multicomponent (Hf0.25Zr0.25Ti0.25Cr0.25)B2 ceramic modified SiC–Si composite coatings: In-situ synthesis and high-temperature oxidation behavior

High-entropy ceramics, a novel type of multicomponent materials with broad application prospects, have stirred up world-wide interests for over a decade. In the current work, in-situ high-entropy (Hf_0.25Zr_0.25Ti_0.25Cr_0.25)B₂ ceramic modified SiC–Si (HETMB₂-SiC-Si) coating was deposited on carbon/carbon (C/C) composites via gaseous reactive infiltration of Si assisted slurry painting (GRSI-SP) method, to improve the oxidation protective ability of C/C composites at 1973 K. The formation and oxidation mechanisms of the coating was explored by first-principles simulation, experiment and thermodynamic analyses. The coating prepared at 2373 K shows dense mosaic structure filled with HETMB₂-rich Si-based multiphase. This coating adheres well with the C/C substrate, which is ascribed to the formed zigzagged SiC–Si transition layer. This coating protected C/Cs from oxidation for more than 205 h at 1973 K. The enhanced oxidation protective ability is mostly ascribed to the subsequently generated compact and stable Hf-Zr-Ti-Cr-Si-O composite oxidation scale. This research will start up novel research ares of developing high-entropy materials modified coatings with improved protective ability under extreme environments.     

Si/CNTs@melamine-formaldehyde resin-based carbon composites and its improved energy storage performances

In this paper, Si/carbon nanotubes@melamine-formaldehyde resin (MFR)-based carbon (Si/CNTs@C) composites have been fabricated by surface modification, electrostatic self-assembly, cross-linking of MFR under hydrothermal treatment and further carbonization. The microstructure of the Si/CNTs@C composites was characterized, and the effects of CNTs content in Si/CNTs@C composites on their electrochemical performances were also investigated in detail. The results indicate Si/CNTs@C composites as anode materials of Li-ion batteries exhibit better high-rate and cycling performances compared to Si and Si@MFR-based carbon composites. Notably, Si/CNTs@C composites with 10.4 wt% CNTs show specific capacities of 1900, 1879, 1,688, 1,394, 1,189 mAh·g⁻¹ at 0.2, 0.5, 1, 2, and 3 A·g⁻¹, respectively. Even at 4 and 5 A·g⁻¹, their capacities still reach 970 and 752 mAh·g⁻¹, respectively. Moreover, they deliver a reversible capacity of 1,184 mAh·g⁻¹ at 0.5 A·g⁻¹ after 100 cycles. Therefore, the reasonable structure is of great significance for enhancing the electrochemical performances of Si-based composites.