MoS2/RGO复合材料的电化学性能和第一性原理研究

利用MoS₂高的理论储锂容量和石墨烯良好的导电性能,采用一步水热法成功制备出卷曲片层状的MoS₂/RGO复合材料,通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱(EDS)、Raman光谱等手段对其进行了结构、形貌、和成分的表征,并通过第一性原理计算了MoS₂和MoS₂/RGO模型的最稳定锂离子吸附位置、电荷密度、差分电荷密度、态密度和扩散能垒。实验结果表明,MoS₂/RGO复合材料在前70次充放电循环中,保持着800 mAh/g以上的高放电比容量,经过100次循环后,放电比容量为515.3 mAh/g,明显高于单一MoS₂(170.8 mAh/g),同时,该复合材料具有优于单一MoS₂的倍率性能,经过1000 mA/g的大电流密度循环后重新回到100 mA/g时,MoS₂/RGO复合材料仍保持在高的放电比容量(941.2 mAh/g)。第一性原理计算结果表明,在石墨烯的作用下,MoS_2<...     

自支撑CC/NiS2纳米片中间层制备与锂硫电池性能研究

多硫离子的穿梭效应是限制锂硫电池发展的一个关键问题。通过水热法和进一步的硫化反应合成了自支撑的碳布/二硫化镍纳米片(CC/NiS₂)复合材料,并将其用作锂硫电池中间层来有效抑制多硫离子的穿梭效应。NiS₂纳米片均匀生长在CC表面,具有较大的比表面积和优异的催化活性,能够显著增强对多硫离子的化学吸附能力并促进电化学反应动力学。相比于碳布(CC)中间层电池,CC/NiS₂中间层电池具有明显提高的倍率性能和良好的循环寿命,在0.5C下放电的初始比容量为1 254 mA·h·g^-1(增加52%),在2C下循环300圈后的比容量仍高达928 mA·h·g^-1,容量衰减率仅为每圈0.015%。     

Ca/Cu共掺杂的O3-NaFe0.5Mn0.5O2钠离子电池正极材料的电化学性能研究

层状过渡金属氧化物由于其较高的理论比容量和较低的经济成本,被视为一种具有良好应用前景的钠离子电池正极材料。采用溶胶-凝胶法和热处理的方式,制备Ca/Cu共掺杂的铁锰基层状氧化物(O3-Na_0.9Ca_0.05Fe_0.45Mn_0.45Cu_0.1O₂)。采用X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等对该O3型铁锰基层状氧化物正极材料进行表征分析。结果表明,在32 mA/g电流密度下该材料具有205.2 m A·h/g的高比容量,循环50圈之后仍具有67.64%的容量保持率,在160 m A/g下循环100圈后依然具有81.4 m A·h/g的放电比容量。由于Ca的掺入,引起Na⁺空位的增加,并且Cu的掺入提高了Mn的价态,从而提高了Na⁺的扩散速率,抑制了Mn³⁺的Jahn-Teller效应,缓解了晶格应力,有效提高了材料的结构稳...     

三维石墨烯包封石墨的储锂性能研究

石墨由于价格低廉、电压平台稳定以及质量比容量高[372 (mA·h)/g]等优势,在锂离子电池领域已被广泛应用,但其存在振实密度较低和循环稳定性较差等不足。利用石墨和氧化石墨烯进行水热反应获得水凝胶,通过石墨烯的毛细收缩和静电自组装原理,获得具有致密结构的石墨烯包封石墨复合块体(石墨@石墨烯),使粉末石墨的振实密度从1.2 g/cm³提高到1.7 g/cm³。与石墨相比,石墨烯构筑的致密三维导电网络结构具有更优异的电化学循环稳定性和倍率性能。在0.01～2.00 V测试电压区间,石墨在0.5 A/g倍率下,经过100圈循环后放电比容量仅保持在227.4 (mA·h)/g,容量保持率仅为64.1%;而石墨@石墨烯复合材料的容量保持在353.9 (mA·h)/g,维持了98%的高容量保持率。证明石墨烯包封石墨可以有效提高石墨的振实密度以及长循环稳定性。     

低热-Na2CO3联合处理生物污泥释放碳源

针对剩余污泥溶胞效率低问题,开展低热-Na₂CO₃联合处理剩余污泥释放碳源的研究。结果表明,相对最佳试验条件下,Na₂CO₃投加量6.0 g/L、试验温度90℃、反应时间24 h,上清液中SCOD (溶解性化学耗氧量)、蛋白质和多糖浓度分别达11 781.78 mg/L、1 289.67 mg/L和537.81 mg/L。通过破解前后SEM照片可知,破解前初始污泥颗粒轮廓清晰,颗粒分明;破解后污泥颗粒表面明显被破坏,出现团聚现象。研究表明,采用低热-Na₂CO₃联合处理能够有效破解污泥,释放碳源。     

Rb掺杂Li4Ti5O12作为锂离子电池负极材料的合成及电化学性能

合成了不同Rb掺杂量的钛酸锂（Li_4-xRb_xTi₅O₁₂; x = 0.010, 0.015, 0.020）作为锂离子电池的负极材料。测试结果显示,Rb离子掺杂有效增强了钛酸锂的电子电导率。相同的测试条件下,相比于未掺杂样品和高Rb含量掺杂样品（x = 0.015, 0.020）,适量的Rb掺杂钛酸锂（Li_3.99Rb_0.01Ti₅O₁₂; x = 0.010）表现出最优的电化学性能。Li_3.99Rb_0.01Ti₅O₁₂材料表现出161.2 mA∙h/g的初始容量,且在1 C下经过1000次循环后容量保持率可达90.9%。此外,全电池Li_3.99Rb_0.01Ti₅O₁₂ // LiFePO₄在0.5 C条件下首次放电容量为144 mA∙h/g,经过150次循环后,容量保持率为78.8%。     

Fe3O4纳米颗粒对玉米秸秆光发酵产氢的影响

以HAU-M1光合菌群作为发酵细菌,以玉米秸秆为发酵底物,研究Fe₃O₄纳米颗粒对光发酵产氢过程的影响。结果表明:粒径60 nm的Fe₃O₄纳米颗粒浓度为100 mg/L时,比产氢量达到(46.68±1.00)mL/g VSS,与对照组的(35.07±0.56)mL/g VSS相比提升(33.11±0.01)%,此时的能量转化率也提高33.10%。产氢动力学分析结果也表明Fe₃O₄纳米颗粒对反应体系有明显的影响,粒径60 nm的Fe₃O₄纳米颗粒浓度为100 mg/L时,最大产氢潜能和最大产氢速率分别为46.97 mL/g VSS和1.06 mL/(g VSS·h)。适宜的Fe₃O₄纳米颗粒的粒径和浓度能显著促进光发酵产氢能力,而浓度过高则会产生抑制作用。     

喷雾干燥法制备石墨烯包覆富锂锰基材料Li1.22Mn0.52Ni0.26O2及其电化学性质

本工作采用喷雾干燥法制备了小片径石墨烯包覆的Li1.22Mn0.52Ni0.26O2富锂锰基材料(G-LNMO),系统研究了包覆前后材料的晶体结构、微观形貌及电化学性质.扫描电镜(SEM)及透射电镜(TEM)结果表明,该方法实现了石墨烯对富锂锰基材料(LNMO)的均匀包覆.充放电测试表明,石墨烯包覆后将LNMO材料在0.1 C和1 C倍率下的放电容量分别从199.8 mA·h/g和87.1 mA·h/g提升至220.2 mA·h/g和117.6 mA·h/g.在0.5 C倍率下经过100次循环后,G-LNMO材料的容量保持率为88％,相比于LNMO材料提升了17％.电池充放电曲线及电化学阻抗分析显示,石墨烯包覆能够显著提升电极动力学,降低电池在充放电过程中的极化,减缓电极/电解液界面副反应的发生,进而提升材料的循环稳定性和倍率性能.     

上转换材料TiO2∶Er3+/Yb3+/Li+的制备及其在玻璃盖板中的应用

采用溶胶凝胶法和旋转镀膜法制备Er³⁺/Yb³⁺/Li⁺掺杂TiO₂胶体和薄膜,确定上转换材料最优制备方案为n(乙酰丙酮)∶n(C₁₆H₃₆O₄Ti∶H₂O)∶n(异丙醇)∶n(Er(NO₃)₃·5H₂O)∶n(Yb(NO₃)₃·5H₂O)∶n(LiNO₃)=1∶3∶9∶70∶0.12∶0.60∶0.15(物质的量之比),水的滴加速率为10 s/滴,溶液pH值为2～3,溶胶呈透明均匀淡黄色。吸收光谱在近红外区峰值明显。可见光透光率最高可达94.42%,较普通玻璃提高1%～2%。光伏组件通过光电转换效率测量系统进行检测,玻璃盖板镀膜后光伏组件的光电转换效率从16.5%升至17.2%,增加约0.7%。研究结果表明,该薄膜可提高玻璃盖板透光率,扩大光伏组件光谱吸收范围...     

一种新型水系锌离子电池正极材料NiCo_(2)O_(4)的制备和电化学性能北大核心CSCD

水系锌离子电池的能量密度高、稳定性好、安全系数高。NiCo_(2)O_(4)材料作为双过渡金属氧化物,其导电性能和电化学活性都很出色,本工作首次采用NiCo_(2)O_(4)材料作为水系锌离子电池的正极。采取了溶胶-凝胶法加煅烧热方法制备出立体尖晶石状的NiCo_(2)O_(4)材料,借助扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能谱分析技术(EDS)和电化学技术等表征测试手段,分析这种新型水系锌离子电池正极材料的形貌和电化学性能。结果表明,立体尖晶石状的NiCo_(2)O_(4)材料有着优良的纯度和结晶性,颗粒分散均匀,没有团聚,无杂质且具有良好稳定的充放电性能。电极在100 mA/g电流密度下,首次放电比容量为92 mA·h/g,100圈充放电测试后放电比容量为60 mA·h/g,200圈后,放电比容量保持在44 mA·h/g。但在循环倍率测试中发现,当电流密度较大时,NiCo_(2)O_(4)电极产生了27 mA·h/g的衰减,在一定程度上有着不可逆的冲击破坏。本研究有助于推动水性锌离子电池电极的应用,为高性能水性锌离子电池电极材料的研发提供实验依据。     

Behavior of the monophosphate tungsten bronzes (PO2)4(WO3)2m (m = 4 and 6) in electrochemical lithium insertion

The electrochemical lithium insertion process has been studied in the family of monophosphate tungsten bronzes (PO₂)₄(WO₃)_2m, where m = 4 and 6. Structural changes in the pristine oxides were followed as lithium insertion proceeded. Through potentiostatic intermittent technique, the different processes which take place in the cathode during the discharge of the cell were analysed. The nature of the bronzes Li_x(PO₂)₄(WO₃)_2m formed was determined by in situ X-ray diffraction experiments. These results have allowed establishment of a correlation with the reversible/irreversible processes detected during the electrochemical lithium insertion. Measurements of resistivity showed that upon lithium insertion, the metallic pristine oxides become insulating.     

MW-assisted synthesis of LiFePO4 for high power applications

LiFePO₄/C was prepared by solid-state reaction from Li₃PO₄, Fe₃(PO₄)₂·8H₂O, carbon and glucose in a few minutes in a scientific MW (microwave) oven with temperature and power control. The material was characterized by X-ray diffraction, scanning electron microscopy and by TGA analysis to evaluate carbon content. The electrochemical characterization as positive electrode in EC (ethylene carbonate)–DMC (dimethylcarbonate) 1 M LiPF₆ was performed by galvanostatic charge–discharge cycles at C/10 to evaluate specific capacity and by sequences of 10 s discharge–charge pulses, at different high C-rates (5–45C) to evaluate pulse-specific power in simulate operative conditions for full-HEV application. The maximum pulse-specific power and, particularly, pulse efficiency values are quite high and make MW synthesis a very promising route for mass production of LiFePO₄/C for full-HEV batteries at low energy costs.     

铜基底上无黏结剂Co3V2O8多孔纳米片阵列的制备以及锂离子电池性能研究

直接在铜基底上生长具有不同金属离子的多孔过渡金属氧化物,成为有前途的锂离子电池电极材料的候选。本文提出了一种简便可行的低温水热沉积方法在铜基底上制备前驱物阵列。前驱物经过煅烧处理得到具有多孔特性Co₃V₂O₈纳米片阵列,多孔纳米片阵列用作锂离子电池负极材料显示出了长期循环稳定性和高倍率性能。在1.0 A/g电流密度下,电池经过240次循环后显示出1 010 mA∙h/g的容量;在3.0 A/g的电流密度下,电池循环600次后显示出552 mA∙h/g的可逆容量。     

Synthesis and electrochemical studies on Al2O3 coated LiNi0.5Co0.44Fe0.06VO4 for lithium ion batteries

LiNi_0.5Co_0.44Fe_0.06VO₄ cathode material has been synthesized by a citric acid:polyethylene glycol polymeric method at 723 K for 5 h in air. The surface of the LiNi_0.5Co_0.44Fe_0.06VO₄ was coated with various wt.% of Al₂O₃ by a wet chemical procedure and heat treated 873 K for 2 h in air. The samples were characterized by XRD, FTIR, SEM, and TEM techniques. XRD patterns expose that the complete crystalline phase occurred at 723 K and there was no indication of new peaks for the coated samples. FTIR spectra show that the complete removal of organic residues and the formation of LiNi_0.5Co_0.44Fe_0.06VO₄. TG/DTGA results reveal that the formation of LiNi_0.5Co_0.44Fe_0.06VO₄ occurred between 480 and 670 K and the complete crystalline occurred at 723 K. SEM micrographs show the various morphological stages of the polymeric intermediates. TEM micrographs of the pristine LiNi_0.5Co_0.44Fe_0.06VO₄ reveal that the particle size ranged from 130 to 150 nm and Al₂O₃ coating on the fine particles was compact and had an average thickness of about 15 nm. The charge–discharge experiments were carried out between 2.8 and 4.9 V (versus Li) at a current rate of 0.15 C. The 1.0 wt.% Al₂O₃ coated sample had the best electrochemical performance, with an initial capacity of 65 mAh g⁻¹ and capacity retention of 60% after 50 cycles. The electrochemical impedance behavior suggests that the failure of pristine cathode performance is associated with an increase in the impedance growth on the surface of the cathode material upon continuous cycling.     

On the reversibility of hydrogen storage in Ti- and Nb-catalyzed Ca(BH4)2

The hydrogen sorption properties of calcium borohydride (Ca(BH₄)₂) catalyzed with a small amount of TiF₃, TiCl₃, NbF₅ or NbCl₅ are investigated using thermal analyses and X-ray diffraction. NbF₅ exhibits the best performance among all the catalysts; it causes a decrease in the hydrogen desorption temperature which leads to hydrogen absorption at practical temperature and pressure conditions. The hydrogen content of Ca(BH₄)₂ with NbF₅ reaches about 5.0 wt.% after hydrogen absorption at 693 K for 24 h under 90 bar of hydrogen. The main dehydrogenation product of Ca(BH₄)₂ with NbF₅ is a CaH_2−xF_x solid solution with a CaF₂ (C1) structure, while pure Ca(BH₄)₂ produces CaH₂ after hydrogen desorption.     

Defect reduction in electrochemically deposited CdS thin films by annealing in 02

Using the electrochemical deposition method, CdS thin films were deposited from acid solutions (pH = 2.5) containing CdS0₄ and Na₂S₂0₃ on indium-oxide coated glass substrates. These films were annealed in N₂, air, or O₂ atmosphere at 200–500°C for 30 min. Photoluminescence spectra were measured at 77 K. For the films annealed in N₂, the band edge emission became weaker and the luminescence due to defects shifted to longer wavelengths as the annealing temperature was raised above 300°C. However, for the films annealed in air or O₂, the band edge emission was observed strongly irrespective of the annealing temperature and the luminescence due to defects was weak. Thus the O₂ annealing is useful for the defects reduction.     

Effect of Na2SO4 additive in positive electrodes on the performance of sealed lead-acid cells for electric scooter applications

This study investigated the effects of Na₂SO₄ additive in the positive electrode on the performance of sealed lead-acid cells. The additive Na₂SO₄ in the cured plates can reduce the 4BS crystal size, which produces a smaller -PbO₂ and β-PbO₂ crystal size in the formed plates, which will have a larger surface area. The plate's chemical composition is independent of the amount of Na₂SO₄ additive in the positive electrodes. Plate composition relies only on the cure temperature conditions. Increasing amounts of Na₂SO₄ additive to the positive electrode will not decrease the crystal size appreciably. The optimal amount of Na₂SO₄ additive is 0.01–0.05 M, which produces the smallest crystal size and largest specific surface area. Cells with Na₂SO₄ additive in the positive plates have a smaller surface area, causing a higher initial capacity and average capacity per cycle for both testing methods: the standard cycle testing and the electric scooter (ES) driving pattern cycle testing. The initial capacity and average capacity can be increased up to 4% in the standard cycle testing and up to 8% in the ES driving pattern cycle testing.     

High-temperature superconductor, YBa2Cu307-x as all- solid-state lithium cell

The utility of the high-temperature superconductor, YBa₂Cu₃O_7-itx, as the cathode material for an all-solid-state lithium cell has been examined. The capacity of YBa₂Cu₃O₇-x, is 223 mA h g⁻¹ and the discharge efficiency is> 92%. Measurements of a.c. impedance show that the charge-transfer resistance at the interface of the electrolyte/cathode is very low and increases with the depth-of-discharge of the battery. Studies using X-ray photoelectron spectroscopy (XPS) reveal that the cathode becomes doped with Li⁺ ions as the cell discharges.