碱性Al-H_2O_2半燃料电池Au/Ni阴极性能研究

以泡沫镍为基体,AuCl3为沉积液,应用快速自沉积法制备了泡沫镍负载的纳米Au/Ni电极.电化学方法测定AuCl3溶液的浓度和沉积时间对Au粒子的尺寸和分布以及以该电极作为Al-H2O2半燃料电池阴极对H2O2性能的影响.实验表明,泡沫镍经2mmol·L-1AuCl3溶液浸渍60s后,其表面完全被粒径小于100nm的Au粒子覆盖;以其为阴极的Al-H2O2半燃料电池,在0.4mol·L-1H2O2溶液中峰值功率达135mW·cm-2.     

Mo-La_2O_3阴极碳化层组织结构研究

采用高分辨透射/扫描电镜,X射线衍射和俄歇探针等分析手段对实用型的FU-6051电子管的碳化Mo-La2O3阴极显微组织结构进行了观察分析。碳化Mo-La2O3阴极碳化层为疏松多孔的Mo2C块状组织,其中有许多垂直于丝轴方向的晶界与孔洞串,相互贯通直至阴极表面。碳化层与芯部基体钼结合良好,两者间无明显的过渡层。活性物质La2O3在阴极的碳化层和基体中分布均匀,但在阴极表面有相当程度的富集。La2O3在碳化层中以两种方式存在:在晶界、孔洞中以微米级的颗粒富集,在Mo2C晶体内部弥散分布纳米级La2O3粒子。     

纳米陶瓷颗粒的电催化效应及其在复合刷镀层中的化学状态

采用循环伏安法和电位阶跃法研究了nano-Al₂O₃ / Ni复合电刷镀体系的电化学响应，探讨了纳米颗粒对复合电沉积的影响；用X射线光电子谱研究了复合镀层中nano-Al₂O₃颗粒与基质金属之间的相互作用。结果表明纳米颗粒能使金属沉积过电位显著降低，电流效率、金属成核率及晶体生长速度增加，从而对金属镍的电结晶表现出明显的催化效应；在金属镍电结晶过程中，部分到达阴极附近的nano-Al₂O₃颗粒被电极表面捕获。金属生长面上的吸附态镍原子到达纳米颗粒与电极表面接触处，与该处纳米颗粒表面的不饱和氧原子形成Ni-O化学键，纳米颗粒与基质镍以化学键形式结合。纳米颗粒与电极表面的结合区域成为新的成核或生长中心，在随后的刷镀过程中纳米颗粒逐渐被电沉积的金属镍包埋，从而形成复合镀层。     

表面修饰纳米二氧化硅及其与聚合物的作用

本文综述了近几年国内外对纳米二氧化硅的表面化学修饰及其在聚合物基纳米复合材料中与基体作用方式的研究工作。对纳米SiO₂进行表面修饰可以改善纳米颗粒与聚合物基体间的亲和性,同时可以使纳米SiO₂表面功能化,有利于SiO₂与聚合物基体间形成强的结合力。纳米SiO₂与聚合物基体间可以以吸附力、氢键、共价键等方式结合,不同的结合方式对材料性能也会产生不同程度的影响。     

熔融碳酸盐燃料电池ZnO/NiO阴极稳定性及电化学性能研究

以ZnO作添加物,采用流延成型法制备了ZnO/Ni复合阴极,研究其微观形貌和相组成,并应用交流阻抗谱研究了ZnO/NiO复合阴极在(Li0.62K0.38)2CO3低共熔盐中的稳定性和电化学性能.结果表明,ZnO/Ni复合阴极和Ni阴极具有基本相近的表面形貌、空隙率和孔径尺寸.ZnO的添加能显著降低NiO在熔盐中的溶解度,其中,2mol%ZnO/NiO复合阴极的NiO溶解度比纯NiO阴极的约低1个数量级,并具有较低的电荷传递电阻(接近于纯NiO值),可望成为MCFC一种很有前景的阴极材料.     

纳米多孔结构镍基复合膜电极的电化学法制备及其电容特性

通过对电沉积法得到的Ni-Cu合金镀层进行电化学去合金化处理, 制备了纳米多孔结构金属镍膜. 采用循环伏安法对多孔金属镍膜在1 mol·L^-1 KOH溶液中进行阳极氧化处理, 获得了纳米多孔结构的镍基复合膜电极. 应用扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和电化学技术对所制备的膜电极的物理性质及赝电容特性进行了表征. SEM、XRD和XPS的测试结果表明, 所制备的纳米多孔结构镍基复合膜由Ni、Ni(OH)₂和NiOOH组成. 电化学实验结果显示, 该复合膜在20 A·g^-1的充放电电流密度下, 给出了578 F·g^-1的初始比电容; 在1000次充放电循环后, 它的比电容值为544 F·g^-1, 电容保持率为94%. 纳米多孔结构有利于KOH电解液的渗透, 从而促进反应物种在电极内部的传输; 纳米多孔的金属镍基体可以提高Ni(OH)₂膜的电子导电性; 纳米大小的Ni(OH)₂颗粒能够缩短质子的固相扩散路径. 上述因素是所制备的纳米多孔结构镍基复合膜电极具有优异赝电容特性的主要原因.     

静电喷雾结合热压处理制备荷负电PVA-SA/PAN纳米纤维基复合滤膜及其纳滤性能研究

以静电纺丝聚丙烯腈(PAN)纳米纤维作为多孔支撑层,以亲水材料聚乙烯醇(PVA)和海藻酸钠(SA)为亲水表层材料,通过静电喷雾技术将亲水表层材料沉积在纳米纤维多孔基膜表面,然后将表层PVA-SA纳米串珠层通过水蒸气加湿辅助热压成膜处理在PAN基膜上软化压延形成完整的致密薄膜,最后经过戊二醛交联制备PVA-SA/PAN纳米纤维基复合滤膜.通过对加湿时间、热压温度、热压时间以及PVA-SA静电喷雾时间等成膜工艺条件和交联条件进行优化制备出结构完整的PVA-SA/PAN纳米纤维基复合滤膜.所制备的复合滤膜荷负电,它对阴离子染料具有较好的过滤效果:在0.6 MPa的操作压力下对100 mg/kg的固绿染料的渗透通量为57.1 L/(m~2h),截留率为96.8%.     

氮掺杂多孔炭负载镍纳米粒子对高温煤焦油的催化加氢转化（英文）

通过对生长在石墨相氮化碳两侧的镍基沸石咪唑酸盐骨架材料进行热分解,制备了一种新型的高活性氮掺杂多孔炭负载的镍基催化剂Ni@N-PC,并将其用于高温煤焦油异丙醇超声萃取物的催化加氢转化。催化剂的镍纳米颗粒主要包裹在碳纳米管的顶端,部分分散在碳纳米薄片表面。以1-萘酚为模型化合物,考察了催化剂在不同反应条件下的催化加氢转化活性,揭示了其催化反应机理。并利用GC/MS分析了高温煤焦油异丙醇超声萃取物及其加氢转化产物。结果表明,1-萘酚在120°C反应2 h有70%转化,在200°C反应2 h后完全转化,高温煤焦油异丙醇超声萃取物经加氢后得到大幅改质。高温煤焦油异丙醇超声萃取物中共检测到180种有机物,其中,含氮有机物33种,含硫有机物11种,含氧化合物39种,而经加氢转化后的产物中未检测到含氧、氮、硫等杂原子化合物,说明催化剂Ni@N-PC具有良好的去除杂原子的性能。经加氢后所有的烯烃、环烯和炔烃饱和,大部分芳烃转化为环烷烃,说明催化剂Ni@N-PC具有较高的催化加氢活性。     

纳米金淀积的多孔硅靶增强样品的激光解吸/电离质谱信号

硅片类型和多孔硅结构的多样性影响了多孔硅表面的激光解吸/离子化质谱(DIOS)(无辅助基质的激光解吸/电离飞行时间质谱(LDI-TOF-MS))数据的重复性和靶的耐储时间。本工作通过在多孔硅的表面淀积金纳米颗粒并将其作为目标靶来增强软物质分子如聚乙二醇和多肽的激光解吸/电离质谱信号。纳米金的淀积钝化了多孔硅表面的Si-H活性基团,增加了靶的耐储时间。用场发射扫描电镜表征了多孔硅淀积金纳米颗粒前后的形貌,用X射线能量色散光谱法分析金的百分含量,结果表明其含量随沉积时间的延长而增加。激光解吸/电离质谱信号的增强可能是由多孔硅及其支持的金纳米颗粒的光学和物理性质引起的,该类型的样品靶在激光解吸/电离飞行时间质谱的应用上结合了多孔硅和金纳米颗粒的双重优势。     

基片温度对LiCoO2薄膜结构与电化学性能的影响

采用射频(RF)磁控溅射技术制备了用于全固态薄膜锂电池的非晶态和多晶LiCoO2阴极薄膜,利用XRD和SEM研究了沉积温度对LiCoO2薄膜结构和形貌的影响,并研究了高温退火后薄膜的电化学性能.研究结果表明,随著基片温度的不同,薄膜成分、表面形貌以及电化学行为有明显差异.室温沉积的薄膜很难消除薄膜中Li2CO3的影响,经过高温退火处理后也无法形成有效的多晶LiCoO2薄膜,而150℃沉积的薄膜经过高温退火后形成了有利于锂离子嵌入的多晶LiCoO2结构,薄膜显示出了较好的电化学性能.     

Effects of current densities on the formation of LiCoO<Subscript>2</Subscript>/graphite lithium ion battery

The activation characteristics and the effects of current densities on the formation of a separate LiCoO₂ and graphite electrode were investigated and the behavior also was compared with that of the full LiCoO₂/graphite batteries using various electrochemical techniques. The results showed that the formation current densities obviously influenced the electrochemical impedance spectrum of Li/graphite, LiCoO₂/Li, and LiCoO₂/graphite cells. The electrolyte was reduced on the surface of graphite anode between 2.5 and 3.6 V to form a preliminary solid electrolyte interphase (SEI) film of anode during the formation of the LiCoO₂/graphite batteries. The electrolyte was oxidized from 3.95 V vs Li⁺/Li on the surface of LiCoO₂ to form a SEI film of cathode. A highly conducting SEI film could be formed gradually on the surface of graphite anode, whereas the SEI film of LiCoO₂ cathode had high resistance. The LiCoO₂ cathode could be activated completely at the first cycle, while the activation of the graphite anode needed several cycles. The columbic efficiency of the first cycle increased, but that of the second decreased with the increase in the formation current of LiCoO₂/graphite batteries. The formation current influenced the cycling performance of batteries, especially the high-temperature cycling performance. Therefore, the batteries should be activated with proper current densities to ensure an excellent formation of SEI film on the anode surface.     

Influence of the PVdF binder on the stability of LiCoO2 electrodes

We report herein on the effect of the PVdF binder on the stability of composite LiCoO₂ electrodes at elevated temperatures in 1 M LiPF₆ EC/EMC solutions at open circuit conditions. The structure and morphology of composite LiCoO₂ electrodes with different combinations of electrode components (LiCoO₂ active material, PVdF binder, carbon black and current collector) were evaluated by Raman spectroscopy, X-ray diffraction and SEM. The content of Co ions in the electrolyte solutions was determined by ICP. A new effect was discovered, namely, a detrimental impact of the contact between PVdF and LiCoO₂ on the stability of the active mass. The formation of surface Co₃O₄ and dissolution of Co ions at elevated temperatures is accelerated at the contact points between the active mass and the binder. The effect of water content in the electrolyte solutions on the stability of LiCoO₂ was also studied. The presence of water (and/or HF) is a necessary condition for the accelerated dissolution of Co ions from the active mass. LiCoO₂ oxidizes the solvents at elevated temperatures thus forming CO₂.     

Olivine LiCoPO4 phase grown LiCoO2 cathode material for high density Li batteries

Olivine LiCoPO₄ phase grown LiCoO₂ cathode material was prepared by mixing precipitated Co₃(PO₄)₂ nanoparticles and LiCoO₂ powders in distilled water, followed by drying and annealing at 120 °C and 700 °C, respectively, for 5 h. As opposed to ZrO₂ or AlPO₄ coatings that showed a clearly distinguishable coating layer from the bulk materials, Co₃(PO₄)₂ nanoparticles were completely diffused into the surface of the LiCoO₂ and reacted with lithium of LiCoO₂. An olivine LiCoPO₄ phase was grown on the surface of the bulk LiCoO₂, with a thickness of ∼7 nm. The electrochemical properties of the LiCoPO₄ phase, grown in LiCoO₂, had excellent cycle life performance and higher working voltages at a 1C rate than the bare sample. More importantly, Li-ion cells, containing olivine LiCoPO₄, grown in LiCoO₂, showed only 10% swelling at 4.4 V, whereas those containing bare sample showed a 200% increase during storage at 90 °C for 5 h. In addition, nail penetration test results of the cell containing olivine LiCoPO₄, grown in LiCoO₂ at 4.4 V, did not exhibit thermal runaway with a cell surface temperature of ∼80 °C. However, the cell containing bare LiCoO₂ showed a burnt-off cell pouch with a temperature above 500 °C.     

Effect of Mg doping and MgO-surface modification on the cycling stability of LiCoO2 electrodes

Two synthetic routes including Mg doping and MgO-surface modification were applied to the preparation of LiCoO₂ showing enhanced reversible cycling behaviour as cathode material in lithium ion batteries. Mg-doped LiCoO₂ was obtained by the citrate precursor method in the temperature range 750–900°C. The surface of LiCoO₂ was modified by coating with Mg(CH₃COO)₂ and subsequent heating at 600°C. XRD, chemical oxidative analysis and electron paramagnetic resonance (EPR) of Ni³⁺ spin probes were used to characterize the Mg distribution in LiCoO₂. Substitution of Co by Mg in the CoO₂-layers was found to have a positive effect on the cycling stability, while Mg dopants in LiO₂-layers did not influence the capacity fade. The accumulation of MgO on the surface of LiCoO₂ improves the cycling stability without loss of initial capacity.     

Surface Lattice Modulation Enables Stable Cycling of High-Loading All-solid-state Batteries at High Voltages

Halide solid electrolytes, known for their high ionic conductivity at room temperature and good oxidative stability, face notable challenges in all–solid–state Li–ion batteries (ASSBs), especially with unstable cathode/solid electrolyte (SE) interface and increasing interfacial resistance during cycling. In this work, we have developed an Al³⁺–doped, cation–disordered epitaxial nanolayer on the LiCoO₂ surface by reacting it with an artificially constructed AlPO₄ nanoshell; this lithium–deficient layer featuring a rock–salt–like phase effectively suppresses oxidative decomposition of Li₃InCl₆ electrolyte and stabilizes the cathode/SE interface at 4.5 V. The ASSBs with the halide electrolyte Li₃InCl₆ and a high–loading LiCoO₂ cathode demonstrated high discharge capacity and long cycling life from 3 to 4.5 V. Our findings emphasize the importance of specialized cathode surface modification in preventing SE degradation and achieving stable cycling of halide–based ASSBs at high voltages.     

The study of carbon nanotubes as conductive additives of cathode in lithium ion batteries

Carbon nanotubes (CNTs), including multi-walled CNTs (MWCNTs) and single-walled CNTs (SWCNTs), are employed as conductive additives in lithium ion batteries. The effects of MWCNTs’ carbon precursors, diameter, and weight fraction on the electrochemical behavior of MWCNTs/LiCoO₂ composite cathode are investigated. Meanwhile, a comparison is made between SWCNTs /LiCoO₂ and MWCNTs/LiCoO₂. Among the three kinds of carbon precursors: CH₄, natural gas, and C₂H₂, MWCNTs prepared from CH₄ are very fit for acting as conductive additives due to their better crystallinity and lower electrical resistance. MWCNTs with smaller diameter favor improving the electrochemical behavior of MWCNTs/LiCoO₂ composite cathode at higher charge/discharge rate owing to their advantage in primary particle number in unit mass. To make full use of LiCoO₂ at higher rate, it is necessary to add at least 5 wt.% of MWCNTs with a diameter 10~30 nm. However, SWCNTs are not expected to be added into LiCoO₂ composite cathode since they tend to form bundles.     

新合成方法制备的LiCoO2正极材料的结构和电化学性能研究

采用新合成方法制备了锂离子二次电池正极材料LiCoO₂。通过ICP-AES、XRD、SEM、电化学方法等测试分析了所合成材料的物理性质和电化学性能，并与商品LiCoO₂材料作了对比研究。同时分别以国产MCMB和石墨作负极活性物质、合成的LiCoO₂作正极活性物质做成锂离子电池，对其电化学性能进行了测试。实验结果表明，所合成的LiCoO₂材料的电化学性能优于其它两种商品LiCoO₂材料，其初始放电容量为155.0 mAh·g^-1，50次循环后的容量保持率达95.3%，而且以此为正极的锂离子电池也表现出优良的电化学性能。计时电位分析结果还表明，合成的材料在充放电循环过程中发生了三次相转变过程，但相变过程具有良好的可逆性。     

Improved thermal stability of LiCoO2 by nanoparticle AlPO4 coating with respect to spinel Li1.05Mn1.95O4

The thermal instability of the LiCoO₂ cathode material was greatly improved by the nanoparticle AlPO₄ coating. The AlPO₄ coating appears to minimize the violent exothermic reaction of the cathode with the flammable electrolytes, resulting in excellent thermal stability even at the overcharged state. Moreover, the results of the overcharge and elevated temperature cycling tests show that, when compared with the spinel Li_1.05Mn_1.95O₄, the AlPO₄ nanoparticle coating results not only in enhanced thermal stability of the cathodes but also in reduced Co dissolution in the electrolytes.     

Enhanced overcharge behavior and thermal stability of commercial LiCoO2 by coating with a novel material

Commercial LiCoO₂ has been modified with MnSiO₄ as a novel coating material. The structures, morphologies, overcharge behaviors and thermal stabilities of the pristine and MnSiO₄-coated LiCoO₂ materials were studied. The MnSiO₄-coated LiCoO₂ had initial discharge specific capacities of 181.1 and 232.2 mAh g⁻¹ within the potential ranges 2.75–4.5 and 2.75–4.7 V (vs. Li⁺/Li), respectively. It was found that the overcharge tolerance of the coated cathode was significantly better than that of the pristine LiCoO₂ under the same conditions – the discharge specific capacities of the coated cathode at upper charge cutoff voltages of 4.5 and 4.7 V were as high as 168.7 and 154.3 mAh g⁻¹, respectively, after 50 cycles. Moreover, DSC showed that the coated LiCoO₂ had a higher thermal stability than the pristine LiCoO₂.     

Synthesis and electrochemical performance of three-dimensionally ordered macroporous LiCoO2

Three-dimensionally ordered macroporous (3DOM) LiCoO₂ was synthesized by colloidal crystal templating method using poly(methyl methacrylate) with the diameter of 232 nm as the template. The effects of roasting temperature on properties of LiCoO₂ cathode materials were investigated by thermogravimetric analysis (TG-DTG), scanning electron microscope, X-ray diffraction, transmission electron microscopy, and electrochemical measurements. The results indicated that the synthesized 3DOM LiCoO₂ calcined at 700 °C had better crystal framework and electrochemical properties. The 3DOM LiCoO₂ samples presented higher rate capacity compared to commercial LiCoO₂ with a specific discharge capacity of 151.2 mAh g^?1 at a current density of 1 C, and 92 % of the specific discharge capacity was retained after 50 charge–discharge cycling.