锂离子电池Si/C复合负极材料的合成与性能

采用球磨-热解工艺制备了Si/C复合负极材料。研究了球磨时间对Si/C复合负极材料结构和电化学性能的影响,并分析了电极的失效机理。研究结果表明,通过球磨可以将纳米硅颗粒均匀分散于石墨基体材料表面,同时,葡萄糖热解后形成的无定形碳使两者紧密结合。球磨3h合成的材料具有最优的电化学性能。以100mA/g的电流密度放电,首次放电容量达到1340mAh/g,首次充放电效率为75.6%,循环50次后,容量保持率为34.2%。     

K_2CO_3添加对提高Si/C负极电化学性能的作用

本文研究了Si/C锂离子电池负极材料中K_2CO_3的添加对提高电极电化学性能的作用及其作用机理。采用恒流充放电测试和电化学阻抗谱(EIS)研究了不同K_2CO_3添加量对Si/C负极电化学性能的影响;通过扫描电镜(SEM)和傅里叶红外光谱(FTIR)等方法分析了K_2CO_3添加对Si/C负极在循环过程中结构和成分变化的影响。研究结果表明,加入K_2CO_3后,由于电极在循环过程中结构稳定性增强以及电极的固体电解质界面(SEI)膜阻抗和电荷转移阻抗减少,使Si/C负极的循环稳定性和倍率性能得到明显提高。     

热解温度对锂离子电池Si/C复合负极材料性能的影响

以酚醛树脂为碳源,采用球磨-热解工艺制备了一系列Si/C复合负极材料,通过XRD、SEM、恒流充放电等测试方法,研究了热解温度对复合材料结构、形貌和电化学性能的影响。结果表明,前驱物经不同的热分解温度得到的复合负极材料,其衍射峰基本与原料硅和石墨的衍射峰相符。随着热分解温度的升高,硅颗粒的分散性得到改善,并与石墨及无定形碳层交错起来形成微孔结构,直接对复合材料的电化学性能产生较大的影响。当热分解温度为1000℃时,合成的Si/C复合负极材料综合电化学性能较好,首次充放电效率可以达到73.1%,以100mA/g放电,循环100周后容量保持率为89.7%,以200mA/g放电,循环100周后容量保持率仍可以达到87.8%。     

NiS2/多孔碳纤维复合电极的制备及其储锂性能

制备长循环稳定、高容量的负极材料是锂离子电池实现大规模储能应用的前提之一。利用静电纺丝技术和水热硫化的方法制备了均匀分布的NiS₂/碳纳米纤维(NiS₂/C)复合材料。作为锂离子电池负极材料,NiS₂/C电极的首次放电比容量为864.6 mAh/g,首次库仑效率为62.7%。其中不可逆容量为322.9 mAh/g,不可逆容量主要由转换反应的部分不可逆及固态电解质(SEI)膜的形成造成的。NiS₂/C复合电极表现出优异的循环稳定性,200 mA/g下150次循环后容量仍然维持在519 mAh/g,容量保持率高达90.4%。此外,在2 A/g大电流密度下,NiS₂/C电极的容量仍高于310 mAh/g表现出出色的倍率性能。借助XRD、SEM及TEM表征,分析发现包裹着NiS₂纳米颗粒的碳纤维,作为良好的导电介质,既可以提高NiS₂的导电性,也可缓解NiS₂脱嵌过程中的体积膨胀,使得NiS₂/C电...     

表面活性剂对纳米SnO2负极材料形貌结构及电化学性能的影响

为了提高SnO_2负极材料的电化学性能,本文以锡酸钠为原料、聚乙烯吡咯烷酮(PVP)、尿素、十二烷基硫酸钠(SDS)分别作为表面活性剂,采用水热法制备了具有纳米结构的SnO_2负极材料.利用扫描电子显微镜(SEM)、X射线衍射(XRD)、电化学测试仪测试了材料的形貌、结构和电化学性质.结果表明,使用不同表面活性剂,可获得不同形貌的纳米结构,并且对材料的电化学性能有较大的影响.当尿素作表面活性剂时,获得了分散较好的球形材料,在0.01~3.0 V,以200 mA/g进行充放电测试,首次放电容量2 256.6 mAh/g,经过50次循环后,放电容量保持在440 mAh/g,表现了较好的循环性能.     

基于工业废料的Si/TiN/TiSi2多相复合锂离子电池负极材料的制备及其电化学性能

Si负极材料理论容量高,但其电子电导率低和脱嵌锂过程体积变化大易粉化,使其循环稳定性和倍率性能差以及高性能硅基锂离子电池负极材料成本高,这均妨碍了其大规模产业化应用.本研究提出以太阳能电池硅片切割废料Si粉和TiN粉为原材料,采用低成本的活性气体机械球磨法制备了一种高性能的Si/TiN/TiSi2多相复合负极储锂材料.研究发现,Si在H2气氛球磨过程中与部分TiN发生反应,原位生成了纳米尺度的TiSi2,TiN和新形成的TiSi2弥散于亚微米尺度的Si基体中.Si/TiN/TiSi2复合材料的电化学性能与TiN的添加量紧密相关.其中,物质的量比Si/0.2TiN的体系具有最佳的电化学性能,在300 mA·g-1电流密度下,其首次可逆容量为2394 mA·h·g-1,首次库伦效率达75.8％,经过200次循环后,容量仍保持1295 mA·h·g-1,保持率高达54％.在2.0 A·g-1电流密度下的可逆容量达到609 mA·h·g-1.机理分析表明:高导电的惰性相TiSi2和TiN弥散在Si基体中不仅有利于电极材料在充放电循环过程中的电子传输,且有效缓冲了Si在嵌脱锂过程的巨大体积变化.这是TiN添加改善硅基复合负极材料电化学性能的主要原因.     

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。     

超临界CO2流体辅助合成Si-Fe-Fe3O4-C复合材料及储锂性能

硅碳负极是未来锂离子电池材料发展的重点方向之一,本文针对传统球磨法制备硅碳负极复合不均匀、界面融合差等问题,提出了一种超临界二氧化碳(scCO₂)流体介质球磨合成Si-Fe-Fe₃O₄-C复合材料的新方法。研究发现,纳米硅和中间相碳微球(MCMB)在scCO₂介质球磨混合过程中,CO₂和Fe反应先得到均匀分散的Si-FeCO₃-C前驱体,然后FeCO₃原位高温固相分解得到Si-Fe-Fe₃O₄-C复合材料。同时,在scCO₂流体渗透下,MCMB剥离成石墨片,并与纳米硅和Fe-Fe₃O₄实现较好的界面融合,Fe-Fe₃O₄的引入显著提升了硅碳负极的储锂容量、循环稳定性和倍率性能,Si-Fe-Fe₃O₄-C复合材料在0.2 A·g?1下100次循环后可逆容量保持在1065 mA·h·g?1。本方法利用超临界流体渗透性好、扩散能力强等特点,合成工艺简便,容易工业化实施,具有商业化开发潜力。      

静电纺丝法制备Si/C复合负极材料及其性能表征

以聚乙烯吡咯烷酮(PVP)作为高分子聚合物配体, 采用静电纺丝法制备了Si/C复合负极材料。利用PVP高温烧结形成的碳作为体积缓冲骨架, 有效地解决了硅在循环过程中的体积膨胀和粉化问题。采用X射线衍射(XRD)、拉曼光谱(Raman)和扫描电子显微镜(SEM)对复合材料的晶体结构及微观形貌进行了研究。结果表明, 材料整体呈纤维状分布, 纤维直径300 ~ 400 nm, Si粒子以“麦穗状”均匀地分布在由无定形碳构成的纤维上。电化学测试结果表明, 复合材料首次充放电的不可逆容量为294.9 mAh/g, 是由于电极与电解液界面间固态电解质(SEI)膜的形成所致。另外, 复合材料在低倍率(0.1C、0.2C和0.5C)和高倍率(1.0C和2.0C)下均具有较高的库伦效率及较好的循环稳定性。     

高容量锂电池负极材料TiNb2O7的合成及其机理

将TiNb₂O₇的前驱体在不同温度(400℃、800℃、900℃、1000℃和1100℃)煅烧,用固相合成法制备TiNb₂O₇负极材料并对其样品进行了TG-DSC、XRD和SEM表征和电化学性能测试。结果表明：在900℃煅烧前驱体,锐钛矿与Nb₂O₅反应的主要产物为Ti₂Nb₁₀O₂₉。Ti₂Nb₁₀O₂₉与金红石反应生成了TiNb₂O₇,生成纯单斜相TiNb₂O₇的最佳条件为在1100℃煅烧6 h。TiNb₂O₇负极材料在0.2C电流密度时初始容量为278.4 mAh/g,初始库伦效率为82.9%。TiNb₂O₇具有良好的倍率容量,在1C循环100次后容量保持率为89%。     

Inerting of magnesium dust cloud with Ar, N2 and CO2

Experiments were conducted on the inerting of magnesium dust with N₂, CO₂, and Ar. Comparing the maximum explosion pressure, maximum rate of pressure rise, and limiting oxygen concentration with different inertants, it was determined that Ar is not the best inert gas under all conditions as commonly believed. N₂ was more effective than Ar as an inertant. CO₂ provided more inerting effect than either Ar and N₂ in low magnesium dust concentrations, although explosibility was increased at higher dust concentrations. Both N₂ and CO₂ as inerting agents showed higher LOC values than Ar. These results indicated that N₂ is a more economical inerting gas than Ar for the tested coarse magnesium dust.     

Facile one-step synthesis of Cu2O@Cu sub-microspheres composites as anode materials for lithium ion batteries

Cu_2O@Cu sub-microspheres composites with a narrow particle size distribution from 300 to 500 nm was successfully fabricated by one-step synthesis through the direct thermal decomposition of copper nitrate(Cu(NO_3)_2) in octadecylamine(ODA) solvent. As anode materials for lithium ion batteries, the Cu_2 O@Cu composites obviously possess high specific capacity, excellent cyclic stability and rate capability. The coulombic efficiency is about 84% in the 1 st cycle and increases significantly up to 97.8% during successive cycles at various current densities. Even under a high current density of 500 m A g~(-1), the discharge capacity of Cu_2 O@Cu composites remains up to 200 m Ah g~(-1). The excellent electrochemical properties are ascribed to the synergistic effect between high electronic conductivity and volume-buffering capacity of metallic copper composited with Cu_2 O.     

Electrochemical reduction of CO2 by Cu2O-catalyzed carbon clothes

Cu₂O cubes with average edge lengths of 640 nm were prepared by a chemical reduction approach. The as-synthesized Cu₂O particles were deposited on carbon clothes for electrochemical characterizations in cyclic voltammetry (CV) and potentiostatic measurements. In 0.5 M NaOH electrolytes saturated with N₂ or CO₂, both the Cu₂O and carbon clothes were stable at the potential range of 0 to − 1.7 V. Comparisons in the current responses from the CV and potentiostatic measurements suggested the Cu₂O with notable catalytic abilities for the CO₂ reduction. The mass activity was estimated at 0.94 mA/mg. Chemical analysis from gas chromatography confirmed the methanol to be the predominant product.     

Catalytic reduction of low-concentration CO2 with water by Pt/Co@NC

The reduction of low-concentration carbon dioxide with water to organic fuels is still a huge challenge. In this study, we successfully designed the partially oxidized cobalt nanoparticles coated by the nitrogen-doped carbon layer (Co@NC) of 2–8?nm via a facile method and then interspersed with different amount of Pt nanoparticles. The Co@NC decorated with 1?wt% Pt exhibits the best ability for CO₂ reduction to CH₄ and a CH₄ production rate of 14.4?μmol·g^?1·h^?1 is achieved. It is worth noting that the system is carried out under low-concentration CO₂ (400?ppm) circumstance without any sacrificial agent, which could be meaningful to the design of catalysts for atmospheric CO₂ reduction.     

Large-scale synthesis of ear-like Si3N4 dendrites from SiO2/Fe composites and Si powders

Large-scale ear-like Si₃N₄ dendrites were prepared by the reaction of SiO₂/Fe composites and Si powders in N₂ atmosphere. The product was characterized by field emission scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The results reveal that the product mainly consists of ear-like Si₃N₄ dendrites with crystal structures, which have a length of several microns and a diameter of 100-200 nm. Nanosized ladder-like Si₃N₄ was also obtained when changing the Fe content in the SiO₂/Fe composites. The Si₃N₄ nanoladders have a length of hundreds nanometers to several microns and a width of 100-300 nm. The ear-like Si₃N₄ dendrites are formed from a two-step growth process, the formation of inner stem structures followed by the epitaxial growth of secondary branches.     

Selective solar-driven CO2 reduction mediated by 2D/2D Bi2O2SiO3/MXene nanosheets heterojunction

Photocatalytic CO₂ reduction reaction (CO₂RR) is an environment-friendly technique for clean fuel generation.Developing low-cost and efficient photocatalyst/cocatalyst systems for boosting CO₂ RR is still a challenge.Herein,a novel Bi₂O₂SiO₃/Ti₃C₂2D/2D heterojunction photocatalysts are successfully prepared by in situ growth of Bi₂O₂SiO₃ on the surface of ultrathin Ti₃     

载体Al/Si比对Cu-ZnO-ZrO2催化剂上CO2加氢合成甲醇的影响

用直接合成法制备了不同铝硅物质的量比Al-SBA-15(β)(β=n(Al)/n(Si)=0,0.02,0.03,0.05)介孔分子筛,并采用浸渍法制备了金属负载量m=35%的CZZ/Al-SBA-15(β)负载型介孔催化剂,考察了Al/Si比对负载催化剂结构和性能的影响。采用N_2吸附-脱附、X射线衍射(XRD)、H_2程序升温还原(H_2-TPR)、CO_2吸附(CO_2-TPD)、NH3吸附(NH3-TPD)和透射电子显微镜(TEM)等手段对样品进行了表征,在固定床反应器上评价了其CO_2加氢合成甲醇的催化性能。实验结果表明,CZZ/Al-SBA-15(β)具有介孔结构,Al的引入不但增加了载体表面酸性位点,同时还提高了催化剂表面铜分散度(DCu%)和铜比表面积(SCu)以及促进了Cu~+-O-Zn活性位的形成,从而大大提高了催化剂的活性。其中CZZ/Al-SBA-15(0.03)催化剂的甲醇选择性达到26%,与不掺铝的CZZ/Al-SBA-15(0)催化剂相比,甲醇选择性提高了11%,但随着掺Al量的继续增加,酸性太强,CO_2吸附能力下降,活性反而降低。