锂离子电池负极材料Si@C/SiOx的制备及其电化学性能

硅理论比容量高, 放电平台低, 是商业化锂离子电池石墨负极的替代材料之一, 但是其充放电循环中体积变化大, 容量衰减迅速, 制约了其商业化使用。本研究通过一步法制备了具有核壳结构的硅@碳/硅氧化物(Si@C/SiO_x), 将其作为锂离子电池负极材料。采用SEM、TEM、XRD、XPS等手段对所制备材料的微观形貌、结构以及组分进行了分析, 并对其进行了相关的电化学测试。结果表明, Si@C/SiO_x核壳材料比Si@C核壳材料具备更优良的电化学性能。在200 mA/g电流密度下, 循环45次后, Si@C的容量保持率为60.2%; 而当C/SiO_x作为Si核外壳时, 200 mA/g电流密度下, 循环45次后, Si@C/SiO_x比容量值为787.2 mAh/g, 容量保持率提高到87.3%。这主要是由于C与SiO_x复合后, 外壳的机械强度大于碳壳, 能够较好地缓冲Si体积膨胀产生的巨大应力, 从而保证结构的完整性, 提高了硅基负极材料的商业化应用的可能性。     

核壳结构Si/C复合负极材料的制备与储锂性能研究

以酚醛树脂包覆纳米硅颗粒后通过碳化处理,制备了具有核壳结构的Si/C复合负极材料,并研究了碳化温度和电极中活性物质含量对储锂性能的影响。透射电子显微镜分析结果表明,该复合材料由厚度为5~15nm的无定型碳壳包覆的硅颗粒组成。电化学测试表明,750℃碳化所得复合材料在活性材料∶粘结剂∶乙炔黑=1∶1∶1(质量比)时,初始放电容量为1836mAh/g(首次库仑效率84.8%),循环50次后仍可保持873mAh/g的可逆容量。此外,具有核壳结构的Si/C复合负极比纯硅负极表现出更好的循环稳定性,这可能是因为碳壳的存在缓解了硅的体积膨胀、改善硅的导电性,在一定程度上保证了Li+嵌入和脱出过程的稳定进行。     

锂离子电池硅/碳复合负极材料的研究进展

负极理论容量最大的硅在充放电过程中,体积过度膨胀粉化导致容量衰减快,成为其作为商用负极材料的最大障碍.碳材料不仅具有一定的电化学活性,结构也较稳定,可以作为硅电极的"缓冲基体";具有高容量和优良循环性能的硅-碳复合负极材料已经成为该领域的研究热点.按照碳材料的分类,评述了Si/C复合电极材料,并初步展望了该领域的研究方向.     

锂离子电池Si/C/石墨复合负极材料的电化学性能

采用热裂解方法, 热解分散于聚偏二氟乙烯溶液中的硅和石墨, 得到了具有稳定电化学循环性能的Si/C/石墨复合负极材料。透射电子显微镜观察发现, 复合材料形貌为无定型碳包裹硅颗粒的核壳结构。通过系统研究不同Si粒径和石墨含量对电极电化学性能的影响, 发现Si颗粒粒径越小复合材料电化学循环稳定性能越优越, 适当的降低石墨含量有利于电极材料剩余比容量的提高。当Si粒径为50 nm, Si与石墨质量比1:1时, 电极材料具有1741.6 mAh/g的首次放电比容量和72.5%的首次库仑效率, 60次循环后, 可逆比容量保持在820 mAh/g。热解有机物形成碳包覆的结构能有效地改善硅基类负极材料的电化学循环性能。     

包覆结构Si/C复合负极材料研究进展

以包覆结构Si/C复合材料作为负极的锂离子电池(LIBs)具有能量密度高、自放电效率低、循环寿命长等特点。然而,锂在硅中插入/脱出过程的体积膨胀和固体电解质界面膜(SEI)的不稳定性,阻碍了硅的商业化应用。本文通过对近年来新型包覆结构Si/C复合负极材料的构筑方法、电化学性能、比容量和循环性能进行分析和研究,发现包覆结构Si/C复合负极材料不仅可以缓解硅在锂化过程中的体积膨胀和炭层破裂,而且可以有效提高LIBs循环稳定性。因此,Si/C复合材料有望取代石墨成为高容量LIBs的主要负极材料。     

源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料

锂离子电池硅基负极材料的理论比容量比传统石墨材料高10倍, 是最有前途的锂离子电池负极材料之一。然而硅基纳米材料的制备工艺复杂、成本高昂, 严重限制了锂离子电池硅负极的商业应用。本工作采用溪木贼为原料, 通过深度还原、浅度氧化和碳包覆工艺制备了三维多孔生物质硅/碳复合材料(多孔3D-bio-Si/C)。三维多孔结构不仅有利于Li⁺的快速传输, 而且提供足够的空隙缓解在脱-嵌锂过程中发生的体积变化。得益于三维结构中大量的孔隙和高强度的外部碳层, 多孔3D-bio-Si/C制备的电极表现出优异的电化学性能。当电流密度为1 A/g时, 多孔3D-bio-Si/C的可逆容量为1243.2 mAh/g, 循环400次后仍可保持933.4 mAh/g, 容量保持率高达89%。利用溪木贼作为生物质硅源制备高性能硅基负极材料, 实现了低成本、可规模化、绿色和可持续的合成路线, 有望为Si基锂离子电池负极材料的商业应用打下基础。     

锂离子电池用硅/石墨/碳复合负极材料的电化学性能

采用湿法混料及高温热解法制备了锂离子电池用硅/石墨/碳复合负极材料,并研究了不同配方的复合材料结构及电化学性能。研究发现,硅含量为20%(质量分数)时,复合材料首次可逆容量为865mAh/g,循环30次后仍为757mAh/g,容量保持率可达88%,大大改善了硅基材料作为锂离子电池负极材料的电化学性能。     

钠离子电池双层碳包覆Na3V2(PO4)3正极材料的超声辅助溶液燃烧合成及其电化学性能

用超声辅助溶液燃烧合成技术制备双层碳包覆的Na₃V₂(PO₄)₃ (NVP)钠离子电池正极材料，并对其电化学性能进行深入的研究。结果表明，双层碳包覆在NVP颗粒表面，由内自外分别为无定形硬碳和石墨烯。石墨烯添加量为5.0%(质量分数)的碳包覆NVP复合材料具有优异的电化学性能，在1 C倍率下充放电其初始比容量为117 mAh·g^–1，循环300圈后容量的保持率为79%，在10 C倍率下其放电比容量高达100 mAh·g^–1。这种正极材料电化学动力学性能的提高，源于均匀的双层碳包覆结构及其构建的三维电子传输通道。     

新型核壳结构硅碳复合负极材料的制备及电化学性能（英文）

通过对氧化硅预处理得到多组分硅pSi(Si、SiO、SiO_2),再利用化学气相沉积法(CVD)设计了具有核壳结构的pSi与碳纳米纤维(CNF)的复合材料(pSi-CNF)。多组分硅中Si、SiO提供电化学可逆容量,SiO_2可以抑制硅的体积膨胀;碳纳米纤维包覆形成的壳层结构可以有效提高复合材料的导电性,同时进一步抑制硅的体积膨胀保持核壳结构的完整。通过SEM、TEM、EDS、XRD、Raman和XPS对复合物的微观结构进行分析。结果表明:pSi-CNF的粒径为5～20μm,碳纳米纤维的直径为5～40 nm, pSi-CNF复合材料中含有Si、SiO和SiO_2多种组分硅,有明显特征峰;碳纳米纤维均匀包覆于硅表面,形成核壳结构。电化学性能测试表明,在0.2 A·g~(-1)的电流密度下,经100次循环后其可逆容量为1 411 mAh·g~(-1),容量保持率为74%,具有良好的循环稳定性和较高的可逆容量;在1 A·g~(-1)的电流密度下,经300次循环后其可逆容量为735 mAh·g~(-1),容量保持率为86%,且具有良好的倍率性能。     

炭涂层硅/石墨烯纳米复合材料的制备及其储锂性能

石墨烯、柠檬酸和硅纳米颗粒的乙醇混合物经超声分散、乙醇挥发和热处理(800℃1h)制备出炭涂层硅/石墨烯(Si@C/G)纳米复合材料。透射电镜表明,Si纳米颗粒的表面形成了一层厚度约为2nm的均匀炭涂层,石墨烯片层支撑着Si@C纳米粒子,且两者具有较强的相互作用。作为锂离子电池负极材料,Si@C/G电极具有较高的库仑效率,在500 mA·g-1的电流密度下,100卷循环后比容量为1431mAh·g-1,表现出优越的循环稳定性。Si@C/G优异的电化学性能归因于石墨烯片层的高导热率、高导电率和优良的机械柔韧性。     

Vibration in a satellite structure with a laminate composite hybrid sandwich panel

The objective of this investigation is to study the complex vibration characteristics of an actual spacecraft structure using the FEA code in conjunction with experimental data. The body of a satellite consists of a monocoque structure formed by joining several composite sandwich panels composed of an aluminum honeycomb core with carbon fiber reinforced laminate skins on both sides.     

Structural studies of a mixed-valence state in the incommensurate composite crystal Sr1.261CoO3

The incommensurate modulated crystal structure of the hexagonal cobalt oxide Sr_1.261CoO₃ has been studied using a four-dimensional (4D) superspace profile analysis of neutron powder diffraction data. Sr_1.261CoO₃ is a composite crystal that consists of the [CoO₃] and [2Sr] subsystems. The [CoO₃] subsystem forms 1D chains that run parallel to the c-axis and consist of face-sharing CoO₆ polyhedra with octahedral (Oh) and trigonal prismatic (TP) coordinations. The structure analysis reveals that the [CoO₃] chains contain 73.9% Oh and 26.1% TP sites, and that the TP sites have longer Co–O bonds than the Oh sites: d_av. =2.039(4) Å (TP) and 1.895(3) Å (Oh). The averaged Co bond valences are Co^3.56(3)+ in the Oh sites and Co^2.45(3)+ in the TP sites, suggesting that a considerable amount of Co³⁺ ions are mixed with Co⁴⁺ions in the Oh sites and with Co²⁺ ions in the TP sites. The observed magnetic susceptibility can be well explained assuming that the compound has the Co mixed-valence state with the spin configurations of S=0 low-spin state for Co³⁺(dε⁶), S=1/2 low-spin state for Co⁴⁺(dε⁵) and S=3/2 high-spin state for Co²⁺(dε⁵dγ²). The Weiss temperature, approximately 0.8 K, implies that Sr_1.261CoO₃ naturally assumes a Curie paramagnetic state, probably owing to the obstruction of the intrachain magnetic interaction by the nonmagnetic Co³⁺ ions. These results suggest that the nonmagnetic Co³⁺ ions play an essential role in the magnetism of Sr_2γCoO₃ systems.     

复杂条件下框架式水塔的爆破拆除

介绍了爆破拆除复杂条件下钢筋混凝土框架水塔的设计方案,在综合考虑楼房结构特点和环境条件的基础上,采用高差与时差相结合的爆破方式,有效地控制了水塔的坍塌范围,对类似工程具有参考价值.     

Structural studies of a mixed-valence state in the incommensurate composite crystal Sr1.261CoO3

Abstract

The incommensurate modulated crystal structure of the hexagonal cobalt oxide Sr_1.261CoO₃ has been studied using a four-dimensional (4D) superspace profile analysis of neutron powder diffraction data. Sr_1.261CoO₃ is a composite crystal that consists of the [CoO₃] and [2Sr] subsystems. The [CoO₃] subsystem forms 1D chains that run parallel to the c-axis and consist of face-sharing CoO₆ polyhedra with octahedral (Oh) and trigonal prismatic (TP) coordinations. The structure analysis reveals that the [CoO₃] chains contain 73.9% Oh and 26.1% TP sites, and that the TP sites have longer Co–O bonds than the Oh sites: d_av. =2.039(4) Å (TP) and 1.895(3) Å (Oh). The averaged Co bond valences are Co^3.56(3)+ in the Oh sites and Co^2.45(3)+ in the TP sites, suggesting that a considerable amount of Co³⁺ ions are mixed with Co⁴⁺ions in the Oh sites and with Co²⁺ ions in the TP sites. The observed magnetic susceptibility can be well explained assuming that the compound has the Co mixed-valence state with the spin configurations of S=0 low-spin state for Co³⁺(dε⁶), S=1/2 low-spin state for Co⁴⁺(dε⁵) and S=3/2 high-spin state for Co²⁺(dε⁵dγ²). The Weiss temperature, approximately 0.8 K, implies that Sr_1.261CoO₃ naturally assumes a Curie paramagnetic state, probably owing to the obstruction of the intrachain magnetic interaction by the nonmagnetic Co³⁺ ions. These results suggest that the nonmagnetic Co³⁺ ions play an essential role in the magnetism of Sr_2γCoO₃ systems.     

Formation of nano-grained structure in a 301 stainless steel using a repetitive thermo-mechanical treatment

In this work effects of the thermo-mechanical parameters were investigated in order to achieve nanocrystalline structure in the as-cast AISI 301 stainless steel. In order to get nanocrystalline structure the repetitive cold rolling and subsequent annealing were used. The cold rolling was carried out at temperatures of 0, - 10 and - 196 °C with strain rate of 0.5 s^− 1 and reduction of 95%, while the annealing treatment was conducted at temperature 600 to 850 °C for 0.5 to 50 min. The results showed that the nanocrystalline austenitic structure with grain size of about 30-40 nm was obtained by annealing at 850 °C for 0.5 min after totally 95% cold rolling reduction at - 10 °C.     

曲梁周期结构隔振器特性研究

利用曲梁具有径向刚度和切向刚度耦合以及波形转换的特性,设计了具有低频宽频带隙的曲梁周期结构隔振器。该隔振器由多层面板-支撑曲梁结构构成。针对曲梁对边支撑的结构,推导了分析含有内部自由度的周期结构的能带结构以及利用子结构迭代法进行响应求解的一般公式,并进行了验证,该子结构迭代法特别适合于周期数较多的复杂周期结构的响应求解。对带隙起始频率和终止频率所对应的结构模态进行了分析。讨论了曲梁和面板结构参数变化对周期结构隔振器带隙结构的影响。并且对一对边支撑的曲梁周期结构隔振器进行试验研究,测得其原点导纳和传递导纳,验证了这种周期结构低频宽频带隙的存在和建模方法的正确性。     

从结构鉴定看照相有机物的发展

本文回顾了近二十几年来感光材料生产技术发展和进步的历程中，在研究开发新型照相有机物方面所取得的重大进展，通过对国外先进彩色胶片中新颖有机物的剖析和结构研究，阐述了当今世界上照相有机物的最新发展动态。     

Substrate-dependent conformational state induced by a hydrophilic group intercalated in a semi-fluorinated molecule

The structure of Langmuir monolayers and Langmuir-Blodgett (LB) films of a semi-fluorinated surfactant containing an intermediate hydrophilic group was investigated. The polar group in the middle of the molecule is shown to induce different conformational states depending on the substrate. At the air-water interface, the molecule adopts a folded shape in order to present its polar group to the water; this leads to a disordered phase. After transfer onto hydrophilic solid substrate (oxidized silicon wafers covered by a behenic acid bilayer), the molecule adopts a stretched conformation and hexagonal packing. Moreover, observed by atomic force microscopy, this LB film displays a labyrinthine morphology induced by the structure of the semi-fluorinated molecule. Finally, the influence of the conformational change of this molecule on its miscibility properties with behenic acid is studied.     

框架结构炼钢厂房的爆破拆除

在框架结构的爆破拆除中，用计算机辅助设计方法确定了柱体的破坏高度。利用导爆管雷管与电雷管组成的混合起爆网络起爆可靠。