Studies on the Electrochemical Behavior of Copper Paratolysulfate and its Complexes

　本文合成了对甲苯磺酸铜,并应用热重(TG)和差示扫描量热法(DSC)进行分析.该铜盐容易脱除全部结晶水,且在空气中不潮解,如与乙醇胺形成等摩尔配合物,则在DMSO和DMF溶剂中能催化1,1′ 联 2 萘酚的氧化,但在H2O或CH3OH溶剂中则不发生反应.此外,还分别研究了该铜盐及其它铜盐与乙醇胺(1∶1)的配合物在DMSO、DMF、CH3OH和H2O中的电化学行为和催化活性.实验表明,铜胺配合物的两步单电子还原过程对催化氧化1,1′ 联 2 萘酚是必要的条件.Copper (II) paratolysulfate has been synthesized and characterized by thermo-gravimetric (TG) measurements and differential scanning calorimetric (DSC) analysis. This salt can easily lose all crystal water and the dehydrated salt does not deliquesce in the air. It is found for the first time that the complex of Cu(p-OTs)_(2)/ethanolamine(1∶1) can catalyze the oxidation of 1,1′-bi-2-naphthol in DMSO and DMF, while the process is difficult to perform in H_(2)O and CH_(3)OH. The electrochemical behaviors of both Cu(p-OTs)_(2) and its complexes with ethanolamine have been studied on platinum electrode in DMSO, DMF, (CH_(3)OH) and H_(2)O respectively. The complexes of various copper salts with ethanolamine are also studied by cyclic voltammetry in different solvents. It is concluded that the two one-electron steps are essential condition for the oxidation of 1,1′-bi-2-naphthol.作者联系地址：中山大学理工学院光电材料与技术国家重点实验室,中山大学理工学院光电材料与技术国家重点实验室 广东广州510275 ,广东广州51027

Protection of WO_3 Electrochromic Films

WO＿3是目前研究最广泛的一种电变色材料，有广泛的应用前景。提高WO＿3膜的稳定性有很重要的实际意义。本文归纳了影响WO＿3膜寿命的因素，提出了改善WO＿3膜的稳定性的策略和保护WO＿3膜的方法。WO_3 is one of the most widely investigated electrochromic materials and has broad prospects For practical applications,In this paper,strategies For increasing the stability of the WO_3electrochromic Films are proposed.Emphasis isplaced on the use of methods For prolonging theoperation liFe of the WO_3 electrochromic Films

Advances in Fuel Cells (Part I)

燃料电池因具有能量转换效率高、污染小的特点而得到广泛的重视。本文综述了燃料电池发展的历史和几类主要燃料电池:碱性燃料电池、酸性燃料电池、融熔碳酸盐燃料电池和固体氧化物燃料电池的研究和应用现状以及发展策略。本文特别介绍了甲醇直接氧化燃料电池研究的进展。Fuel cells had Features of high energy eFFiciency and less enviromental impact which met the requirements of the new power system.The development and practical application of Fuel cells had been promoted worldwide.The recent advances in Fuel cells including A C,PAFC, PEFC,MCFC and SofC were reviewed.The research status of the direct methanol oxidation Fuel cell was also presented

Advances in Fuel Cells

2.4固体氧化物电解质燃料电池(SOfC)SOfC是类似于MCfC的高温燃料电池,但使用固体电解质。由于fOfC在1000℃左右工作,使它具有以下一些优点:(1)在那么高的温度下,所有燃料都会自动地进行内部重整并迅速地氧化成最终产物;(2)由于S工作在高温下,燃料中的杂质对其影响很小,比如燃气中若含50PPMH_2S,电池的电压只下降5%,且对电池本身没什么损害。即可以使用非经处理的燃气。(3)固体氧化物很稳定,在电池工作条件下不存

Electrocatalytic Oxidation of Glucose on Nano Pt/C Electrode

用交替微波法制备纳米PVC催化剂,研究和比较葡萄糖在光亮Pt和纳米Pt/C电极上的氧化行为.实验表明,Pt纳米化后,电极反应过电位降低,动力学速率相应提高,从而使电化学性能得到改善.其催化活性和抗毒化能力大于光亮Pt的可能原因即在Pt纳米化后,大幅度提高了表面积,结果不仅增加其电极活性,而且含氧物也容易接近受毒化的反应点,从而较易氧化毒化物而使电极再次活化.Nano Pt/C electrocatalysts were prepared by intermittent microwave heating method.The electrooxidation of glucose on smooth Pt and～Pt/C electrodes has been studied and compared.The results showed that the electrochemical properties on nano Pt/C were improved due to the reduction of the overpotential and the increase in the kinetic rate.The surface area would be significantly increased when the particle size of the catalyst was reduced to nano-scale,resulting in the increase in the activity.The enhancement in the resistance to poisoning could be explained that the oxygen-containing species are easier to react with poisoning species on nano Pt/C and re-active the electrode.作者联系地址：漳州职业技术学院食品与食品生物工程系,中山大学物理科学与工程技术学院,中山大学物理科学与工程技术学院 福建漳州363000,广东广州510275,现在通讯地址:华南理工大学理学院,广东广州,广东广州510275Author's Address: l,WEI Xiao-lan~**2,SHEN Pei Kang~*21.Department of Foodand Bioengineering,Institute of Technology of Zhangzhou,Zhangzhou 363000,Fujian,China,2.School of Physics and Engineering,Sun Yat-Sen University,Guangzhou 510275,Guangdong,Chin

Study of the Electrooxidation of Glycerol on Oxide and Pd/C Composite Catalysts

应用交替微波加热法制备碳载氧化物和Pd的复合催化剂,并以电化学方法研究这一新型催化剂在碱性条件下对甘油的氧化性能.实验表明,Pd/C催化剂对甘油的电化学氧化有较好活性,但氧化物复合的非铂催化剂对甘油的电化学氧化显示出更高的活性,相对于Pd/C催化剂,其氧化起始电位发生负移及峰电流大幅度提高.本工作还优化了氧化物与Pd的比例.结果证明,氧化物的加入使复合催化剂对甘油氧化产生了协同效应.Oxide and Pd on carbon composite catalysts have been prepared by intermittent microwave heating(IMH) method.The performance of the catalysts for glycerol oxidation in alkaline solution is studied by electrochemical techniques.It is shown that the Pd/C catalyst is active for glycerol electrooxidation.However,the oxide-Pd/C catalysts are even better in terms of the onset potential that is more negative and peak current density.The ratio of oxide to Pd is optimized according to the electrochemical measurement.The results reveal that the addition of oxide into the Pd/C induces the synergistic effect for glycerol electrooxidation.作者联系地址：中山大学光电材料与技术国家重点实验室物理科学与工程技术学院,中山大学光电材料与技术国家重点实验室物理科学与工程技术学院,中山大学光电材料与技术国家重点实验室物理科学与工程技术学院 广东广州510275,广东广州510275,广东广州510275Author's Address: *State Key Laboratory of Optoelectronic Materials and Technologies,School of Physics and Engineering,Sun Yat-Sen University,Guangzhou 510275,Guangdong,Chin

Study on MXene-Carbon Black/Sulfur Composite in Integrated Electrode of Lithium-Sulfur Batteries

锂硫电池的实际能量密度不高和多硫化物（LiPSs）的穿梭效应等问题严重影响了该电池的实际应用。本文通过将二维的Ti3C2Tx Mxene纳米片与碳黑/硫（CB/S）材料进行混合,制备了Ti3C2Tx-CB/S正极材料并将其涂覆在商业隔膜（PP）上,最终获得了Ti3C2Tx-CB/S-PP一体式电极并用于锂硫电池。利用Ti3C2Tx纳米片对CB/S进行修饰,不仅能提高活性物质硫的导电性,还能对扩散的LiPSs进行物理阻挡和化学吸附。而一体式电极的设计有利于提高电池的能量密度。恒流充放电测试结果表明,Ti3C2Tx-CB/S-PP电极在0.1 C电流下的初始放电容量为1028.8 mAh·g-1,高于不含Ti3C2Tx的CB/S-PP电极的896.8 mAh·g-1。Ti3C2Tx-CB/S-PP电极还展示出了比基于传统铝箔集流体的Ti3C2Tx-CB/S-Al电极更好的循环稳定性,前者在0.5 C下400圈长循环测试中的每圈衰减率为0.072%,而后者则为更高的0.10%。本文利用Ti3C2Tx-CB/S构建一体式电极的策略为实现高性能和高能量密度的锂硫电池提供了新的研究方向。Lithium-sulfur (Li-S) batteries are considered as a promising energy storage device due to their ultrahigh theoretical energy density of 2500 Wh·kg-1 and low cost. However, the practical application of Li-S batteries is seriously limited by their low actual energy density, the shuttle effect of polysulfides (LiPSs), and the insulating nature of sulfur and lithium sulfides. Carbon materials have been developed in the design of sulfur hosts due to their adjustable pore structure and high electrical conductivity, but their non-polar surfaces have weak interactions with LiPSs. Herein, MXene-carbon black/sulfur (Ti3C2Tx-CB/S) composites were prepared and applied to the integrated electrodes of Li-S batteries. The CB/S was prepared via a melting-diffusion method and Ti3C2Tx MXene nanosheets were synthesized by etching Ti3AlC2 MAX with LiF/HCl. After mixing CB/S and Ti3C2Tx , Ti3C2Tx-CB/S cathode material was obtained and coated on commercial separator (PP) to prepare Ti3C2Tx-CB/S-PP integrated electrodes. On the one hand, the two-dimensional Ti3C2Tx nanosheets dispersed in the CB/S particles not only serve as multiple physical barriers to inhibit the diffusion of LiPSs, but also have strong chemical interactions with them, effectively alleviating the shuttle effect. Thus, Ti3C2Tx improves the conductivity of CB/S composite, which is beneficial to the reaction kinetics of the cathode. Furthermore, the design of Ti3C2Tx-CB/S-PP integrated electrode increases the energy density of Li-S batteries. X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were employed to analyze the structures, morphologies, and surface chemical composition of the synthesized materials. The results of constant current charge/discharge tests showed that Ti3C2Tx-CB/S-PP electrode achieved superior rate performance and cycling performance than CB/S-PP electrode. The initial discharge capacity of Ti3C2Tx-CB/S-PP electrode at 0.1 C current was 1028.8 mAh·g-1, higher than 896.8 mAh·g-1 of CB/S-PP electrode. The cycling test at 0.2 C indicated that Ti3C2Tx-CB/S-PP maintained a discharge capacity of 726.4 mAh·g-1 after 80 cycles, better than CB/S-PP (529.2 mAh·g-1). Moreover, due to the improved utilization of the active material at the interface between the cathode and the separator, Ti3C2Tx-CB/S-PP electrode also showed better cycling stability compared to the Ti3C2Tx-CB/S-Al electrode based on the traditional aluminum foil current collector. The capacity degradation rate of Ti3C2Tx-CB/S-PP was only 0.072% per cycle in a long-term cycling test of 400 cycles at 0.5 C, while that of Ti3C2Tx-CB/S-Al was 0.10%. The strategy of using Ti3C2Tx-CB/S to construct an integrated electrode provides a new direction for Li-S batteries with high performance and high energy density.广西重点研发计划项目(AB16380030);广西创新驱动重大专项(AA17204083);国家自然科学基金-联合基金重点研发项目(U1705252)通讯作者:沈培康E-mail:[email protected]:Pei-KangShenE-mail:[email protected].广西大学可再生能源材料协同创新中心,广西 南宁 5300042.广西大学化学化工学院,广西 南宁 5300041. Collaborative Innovation Center of Sustainable Energy Materials, Guangxi University, Nanning 530004, Guangxi, China2. School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, Chin

An in situ Fourier Transform Infrared Spectroelectrochemical Study on Alcohols Electrocatalytic Oxidation at Pd Electrode in Acidic Solution

应用电化学循环伏安法(CV)和现场红外光谱(FTIR),研究了酸性溶液中钯催化甲醇、乙二醇电氧化的过程.结果表明:在酸性和中性介质中,甲醇和乙二醇在多晶Pd电极上氧化须在1.5V以上才能发生.随着溶液pH值的降低,过电位减小且峰电流密度上升.溶液的pH值以及电极表面形成的吸附含氧物种对Pd电催化氧化醇有显著的影响.现场红外光谱电化学测试显示,在高电位和强酸性介质中,乙二醇在Pd电极上的氧化产物主要是CO2和少量的乙二酸.在酸性和中性介质中,无论在低电位或高电位,甲醇和乙二醇在Pd上氧化的主要产物是CO2,没有发现CO的存在,说明该氧化过程CO2是经过非毒化的路径产生的.The methanol and ethylene glycol electrooxidation on palladium electrode in acidic solution has been investigated by cyclic voltammetry and in situ Fourier transform infrared spectroelectrochemistry. It shows that the oxidation of methanol and ethylene glycol at Pd electrode cannot proceed until over 1. 5 V in acidic and neutral media. The overpotential decreases and the peak current density increases with the reduction in pH values. The formation of the oxygen-containing species significantly affects the alcohol oxidation on Pd electrode. The in situ FTIR spectroscopic measurements show that the oxidation products of ethylene glycol on Pd electrode are CO2 and oxalic acid at high potentials and concentrated acid solution. However,the dominant product is CO2 for the oxidation of both methanol and ethylene glycol in acidic and neutral solutions,indicating that the pathway of methanol or ethylene glycol oxidation is a non-poisoning process.作者联系地址：中山大学广东省低碳化学与过程节能重点实验室,光电材料与技术国家重点实验室;Author's Address: The Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province,The State Key Laboratory of Optoelectronic Materials and Technologies,Sun Yat-sen University,Guangzhou 510275,Chin

Hydrothermal Reduction Synthesis of LiFePO_4 and Its Electrochemical Performance

以可溶性三价铁盐FeCl3为铁源,Fe粉作还原剂,应用水热还原法合成LiFePO4.XRD、红外光谱及SEM形貌表征表明,在水热条件下,铁粉能完全将三价铁还原为二价铁,得到单一相LiFePO4,且其颗粒团聚形成花簇状;而LiFePO4经过葡萄糖的热解包覆碳生成LiFePO4/C后,颗粒转变似球状.电化学性能测试结果表明,虽然单相LiFePO4的放电容量很低,但LiFePO4/C却表现出良好的倍率性能和循环稳定性.The cathode materials of LiFePO4 were prepared via a hydrothermal reduction method using FeCl3 as Fe source and iron as a reducing agent.The results showed that ferric salt could be reduced to ferrous salt completely under the hydrothermal condition and pure-phase LiFePO4 was obtained based on the test results of XRD and FTIR.Carbon-coated LiFePO4 was synthesized by pyrolysisng glucose at high temperature.The morphologies of pure LiFePO4 displayed cluster-like while the LiFePO4/C displayed sphere-like particles.The electrochemical test showed that the LiFePO4/C had good rate performance,while LiFePO4 delivered much lower discharge capacity.作者联系地址：中山大学光电材料与技术国家重点实验室物理科学与工程技术学院;Author's Address: The State Key Laboratory of Optoelectronic Materials and Technologies,School of Physics and Engineering,Sun Yat-Sen University,Guangzhou 510275,Chin

Nanosized Fe2O3 on Three Dimensional Hierarchical Porous Graphene-Like Matrices as High-Performance Anode Material for Lithium Ion Batteries

采用简单的水解、热处理方法合成三氧化二铁（Fe2O3）负载在三维多级孔类石墨烯（3D HPG）上的复合材料. 3D HPG有效的导电网络有利于负载纳米Fe2O3，使其呈均匀分散状态，并有效增强纳米复合物的导电率，提高Fe2O3利用率，抑制纳米Fe2O3的团聚，从而制得稳定、高性能的锂离子电池负极材料. Fe2O3-3D HPG电极在50 mA·g-1电流密度下首次放电容量达1745 mAh·g-1，50周期放电容量保持于1095 mAh·g-1.Ferric oxide (Fe2O3) as a promising anode material for lithium ion battery is due to its high theoretical capacity (1007 mAh·g-1), earth abundance and low cost. The nanosized Fe2O3 on the three dimensional hierarchical porous graphene-like network (denoted as Fe2O3-3D HPG) has been synthesized by homogeneous precipitation and heat treatment. The 3D HPG can provide a highly conductive structure in conjunction to support well contacted Fe2O3 nanoparticles, and effectively enhance the mechanical strength of the matrices during volume changes, as well as improve the utilization rate of Fe2O3 and suppress the aggregation of Fe2O3 nanoparticles during Li ion insertion/extraction. As a result, the first discharge capacity of Fe2O3-3D HPG was up to 1745 mAh·g-1 at 50 mA·g-1, and after 50 cycles, the retention of the capacity was 1095 mAh·g-1.国家自然科学基金项目（No. 21073241，No. 51210002）资助作者联系地址：中山大学 光电材料与技术国家重点实验室，物理科学与工程技术学院，广东 广州510275Author's Address: State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-sen University, Guangzhou 510275, China通讯作者E-mail：[email protected]