固体氧化物燃料电池中的电解质

综述了固体氧化物燃料电池（SOFC）中固体电解质的研究概况,分析了ZrO2基、CeO2基、Bi2O3基固体电解质和掺杂的LaGaO3为代表的钙钛矿结构的固体电解质的优缺点以及作为SOFC电解质存在的问题,中低温度下稳定的高离子电导率的固体电解质的研制开发及固体电解质的薄膜化研究是降低S0FC工作温度的两个重要途径。     

Ti~(4+)掺杂对Na-β"-Al_2O_3固体电解质电性能的影响

Na-β"-Al2O3固体电解质材料的Na+电导率直接影响着钠硫电池的性能。以提高Na-β"-Al2O3固体电解质材料Na+电导率为目的,利用传统固相反应法,在Li+掺杂作为稳定剂的基础上,加入0%～1. 25%(质量分数)TiO2引入Ti4+,制备Na-β"-Al2O3固体电解质材料。采用X射线衍射(XRD)以及扫描电子显微镜(SEM)对样品进行表征,采用交流阻抗法测试了样品的电导率。实验结果表明,Ti4+掺杂可较大幅度提高Na-β"-Al2O3材料的Na+电导率,原因有三:一是Ti4+掺杂进入Na-β"-Al2O3晶格取代了Al3+,掺杂后抑制了β"相向β相的转变,从而提高β"相的相对含量,且无杂相生成;二是Ti4+掺杂可以降低材料的烧结温度,促进晶粒生长,从而提高了材料的体积密度;三是Ti4+掺杂可以降低材料在高温烧结过程中钠组分的挥发,提高材料的钠含量。其中,在TiO2掺杂量为0. 75%,烧成温度为1575℃,保温0. 5 h条件下,制得的材料性能最佳,电导活化能为0. 1606 eV,离子电导率由未掺杂样品的0. 023 S·cm-1提升至0. 034 S·cm-1。     

改进固相法制备钙钛矿结构La1-x Srx Ga1-y Mgy O3-δ及其性质研究

采用改进固相法合成了具有钙钛矿结构的中温固体电解质La0.9Sr0.1Ga0.8Mg0.2O3-δ(LSGM),用TG-DTA和X射线衍射仪分析了LSGM材料中钙钛矿相的形成过程,利用SEM、交流阻抗谱等检测技术,对LSGM电解质结构及电性能进行表征.XRD分析表明,随着温度的升高,粉体中杂相含量越来越少,在1450℃烧结后形成了单一的钙钛矿相结构.交流阻抗谱检测表明,烧结样品具有稳定的离子电导性能,在800℃时,电导率约为6.8×10-2S/cm.     

La_(0.8)Zn_(0.2)MnO_3固体电解质的制备及导电性能

以Mn(NO3)2、La(NO3)3.6H2O和Zn(NO3)2.6H2O为原料,通过溶胶-凝胶法制备单一钙钛矿结构La0.8Zn0.2MnO3(LZMO)。对合成后的LZMO凝胶进行自蔓延燃烧。XRD分析表明,高于873K煅烧后得到的LZMO,粉体形成了钙钛矿结构且没其他杂相。在673~973 K条件下,空气气氛中,用两端阻塞的交流阻抗方法研究了由1 073 K煅烧所得的钙钛矿材料LZMO离子导电性能,表明了该材料在中高温条件下已经具有了非常好的离子导电性能,673~973 K固体电解质的导电率为1.3×10-3~7.4×10-2Ω-1.m-1。应用Arrhenius公式对离子导电的活化能进行计算,求得离子导电活化能为70.17 kJ/mol。     

新能源汽车反钙钛矿型锂离子固态电解质掺杂改性研究

传统锂离子电池液态电解液具有可燃性，存在安全隐患。随着对二次电池安全性能要求的提升，固态电池近年来成为新型二次电池发展的热点。在所有类型的固体电解质中，反钙钛矿型电解质具有前驱体成本低廉，易于合成以及加工性能好的优点，因此引起了广泛的注意。然而，反钙钛矿型电解质的离子电导率较低，室温下仅为10^-6～10^-5S/cm，从而限制了其在新能源汽车上的应用。实验采用溴镁共掺杂的方法来提高反钙钛矿型电解质的离子电导率。通过溴掺杂氯位以及镁掺杂锂位能够引入更多的锂空位，从而降低了锂离子迁移的活化能，使反钙钛矿型电解质的离子电导率提升4.5倍。最后，以钴酸锂为正极活性材料组装金属锂固态电池，反钙钛矿基固态电池在2C倍率下循环100圈后容量保持率可达90.1%。     

稀土对α-K7[SiFe3(OH2)3W9O37]多金属氧酸盐化学扩渗和导电性的影响

用改进方法合成了标题化合物。采用气相法通过固-气反应,研究多组分稀土对所合成多金属氧酸盐的化学热扩渗。经ICP、XPS、IR和XRD分析发现,微量的La、Ce、Sm、Gd等稀土元素可以渗入到多金属氧酸盐的体相。扩渗后化合物的电导率在室温下σ值达到1.59×10-3S·cm-1,比扩渗前多金属氧酸盐的电导率(σ=2.4×10-7S·cm-1)提高了几千倍;且渗后化合物导电性能的稳定温度显著增大,同导电性能最好的多金属氧酸盐H3PM12O40·29H2O(M=W,Mo)相比,其导电热稳定温度增大近200K,成为在523K以上依然保持高电导率的新型固体电解质。     

热压烧结制备Li3/8Sr7/16Ta3/4Hf1/4O3钙钛矿型固体电解质

采用热压烧结制备了Li_3/8Sr_7/16Ta_3/4Hf_1/4O₃钙钛矿型固体电解质, 研究了不同烧结方式对样品性能的影响。通过X射线衍射仪表征材料的晶体结构, 扫描电子显微镜观察组织形貌, 交流阻抗仪测试电化学性能。结果表明:样品为立方KTaO₃相, 热压烧结成功合成了钙钛矿结构固体电解质, 相对于常压烧结, 热压烧结制备的样品孔隙更少, 晶粒之间结合更加紧密, 致密度高达94.0%, 离子电导率为4.33×10-4S·cm(T=298K).      

Ce0.8Sm0.1Gd0.1O1.9电解质的制备及其性能研究

通过凝胶浇注法制备了Sm, Gd共同掺杂的CeO2(SGC)粉末, 将制得的粉末经1400 ℃高温烧结4 h得到相应的SGC电解质烧结体, 并对SGC粉末及相应的烧结体的性能进行了表征. 实验结果表明: 凝胶浇注法制备出了Sm, Gd共同掺杂的纳米CeO2粉末;所得粉末有良好的烧结活性, 1400 ℃下烧结所得电解质材料的相对密度大于94%. 电导率的测试表明, SGC电解质材料在中温范围有较高的电导率, 800 ℃时, 其电导率达到了0.082 S·cm-1, 有望成为中温固体氧化物燃料电池的电解质材料.     

贵金属掺杂复合稀土氧化物的TPR研究

采用爆炸法合成系列钙钛矿结构复合氧化物La(RhMn)O3。利用程序升温还原法(H2-TPR)测试贵金属(Rh)掺杂复合稀土氧化物(LaM-nO3)的催化特性。结果表明,掺杂Rh后,低温还原峰峰温逐渐降低,钙钛矿的氧化性质发生了变化,氧缺陷和易移动的晶格氧增多。当掺杂少量Rh(0.2)后催化剂对H2的氧化温度明显降低,同时氧化能力明显提高。当Rh掺杂增加到一定量后,H2-TPR谱的高温还原峰面积和峰温又逐渐上升,钙钛矿结构趋于稳定。     

稀土掺杂对LaSrCoO4催化剂性能的影响

采用聚丙烯胺溶胶-凝胶法制备了类钙钛矿La0.7Nd0.3SrCoO4和La0.7Ce0.3SrCoO4复合氧化物催化剂,考察了它们对CO和C3H8的催化氧化活性,并运用XRD,IR,TPR和TPD等手段对催化剂进行了表征.结果表明,稀土掺杂后的LaSrCoO4复合氧化物均为K2NiF4型结构,不同稀土掺杂对LaSrCoO4复合氧化物的CO和C3H8氧化活性的影响不同,Nd掺杂能增加Co3+、化学吸附氧和晶格氧的数量,提高复合氧化物的活性.     

China's Major Non-ferrous Metals Imports & Exports

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Zinc Production by Province in 2014

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80% of Chinese Firms Purchasing Overseas Mines Ended up in the Red

<正>Minmetals Resources acquired the world’s largest copper mine under construction for USD5.85 billion.One after another,listed companies Jien Nickle,China Molybdenum and Chihong Zinc and Germanium raised money to get involved in overseas mining projects…SOEs and private enterprises are engaged in a frenzy of overseas mine purchasing.A reporter with Economic     

Copper Processing Profit Dropped Sharply,Copper Consumption Will Face Impact in the Second Half of the Year

正Judging from China’s copper consumption field,the biggest consumption unit is electric power,which accounts for 47%of total consumption;it is followed by light industry sector,including household electrical appliance,machinery,durable goods and hardware etc,which accounts for 22%of total consumption;followed by transportation field,     

Central Geological Prospecting Fund Newly Added 16.47 Million Tonnes of Bauxite in 2013

正In 2013,the Central Geological Prospecting Fund(CGPF)Project newly discovered 15 ore fields,including 3 large above ore fields,and 5medium sized ore fields.The reporter learned from the recently published"Annual Report of Central Geological Prospecting Fund Project(2013)"that,from 2006 to 2013 the CGPF     

Manufacturers of Copper Tube for Central Air Conditioner Use Face Mounting Pressure in the Final Quarter of the Year

正This year,the investment growth rate of real estate industry continued to slow down,sold area of commercial housing also dropped significantly,which brought huge pressure to the domestic air conditioning manufactures.In the first half of the year,by relying on high growth in national financial expenditure,along with investment in public infrastructure     

Xinjiang Ranks No.1 in Production of Primary Aluminum in China

正Kang Yi,Honorary Chairman of China Nonferrous Metals Industry Association,said recently at the Forum on Development of the Non-ferrous Metals Industry in Central and Western China held in Zhengzhou that,as more and more electrolytic aluminum factories in Xinjiang came into operation,the electrolytic aluminum output of Xinjiang had reached2,275,000 tons in the first 7 months this year,     

Shenhuo Coal Industry and Electricity Power Completed800,000 t/a Aluminum Project in Xinjiang

正"Xinjiang project has been completed according to schedule,but total completion and total start of production are two different concepts,after completion it still needs a gradual process of reaching production target."On the morning of November 3,Shenhuo Coal Industry and Electricity Power told investors the above statement on the investor interaction platform.     

Guangdong Metal Transaction Center has Become the Second Largest Precious Metal Transaction Platform Nationwide

正The reporter learned from Guangdong Province Precious Metal Transaction Center that in 2013the Center maintained healthy development momentum,and had become the second largest precious metal transaction platform in China in terms of market size;currently Guangdong is quickening steps of financial innovation for the Center,aiming to build a transaction center with international core competitiveness.     

Seven Rare Earth Projects Involving Close to 3 Billion Yuan Investment Landed In the HighTech Zone

正On May 22,Baotou Rare Earth Industry Cooperation Consultation MeetingProject Agreement-signing Ceremony was held in Ningbo,nearly 40 enterprises from Ningbo,Guangdong,Hunan,and Shanxi participated in project consultation.After multi-lateral communication,agreements were signed for a total of 7 rare earth projects successfully.