Purification of supporting electrolyte Tetra-n-butylammonium hexafluorophosphate (TBAPF6) English ： A17196 Tetra-n-butylammonium hexafluorophosphate (TBAPF6), 98%, CAS 3109-63-5,is common supporting electrolyte in electrochemistry test. Alfa corp sell it of 98% purity. According our lab’s experience, there was impurity in the raw commercial material, which meet rough electrochemistry rather than explicit test, e.g. OSWV of open-hole fullerene. We’d better to purify it by recrystalization. Two method: 1) recrystallization by ethanol and water. 2) recrystallization by absolute ethanol three times, however, recrystallization once is enough to common test. The recrystallization condition is : 25 g TBAPF6 was dissolved heatedly in 100mL EtOH, cooled down naturally , then cooled in fridg at -16 degree, filtered, dried in vacuo for 24~48h. Yield, 97%. References: 1 ） Purification of Laboratory Chemicals (4th Edition) 2)Robert L. Bedard, Lawrence F. Dahl, "Electrochemical analysis of biocapped triangular cobalt cyclopentadienyl clusters, n (x = 0, 1, 5), containing mixed .pi.-acceptor X and .pi.-donor Y capping ligands : pronounced variations in redox behavior as a function of coordinating ligands", Journal of the American Chemical Society, 1986, 108, 5933. 中文： A17196 Tetra-n-butylammonium hexafluorophosphate, 98% CAS 3109-63-5, 四正丁基六氟磷酸铵 , TBAPF6 是常用的支持电解质， Alfa 有 98% 的物质销售， 25g 400 元。据本实验室经验， Alfa 所售是有杂质的，对于高精度的电化学测量，比如说开孔富勒烯的 OSWV 测量是有影响的，这时需要对其进行纯化。 有两种纯化方法： 1 ） EtOH 和水重结晶。 2 ）无水 EtOH 乙醇重结晶三次，不过在我们实验室中发现重结晶一次足以应对我们的电化学实验室，条件为 25g TBAPF6100mL 乙醇 (EtOH) ，热溶，几乎全溶，自然冷却后冰箱冷冻 -16 度进一步析出，抽滤，真空干燥 24~72h, 收率 97% 。 参选文献 ： 1 ） Purification of Laboratory Chemicals (4th Edition) 2)Robert L. Bedard, Lawrence F. Dahl, "Electrochemical analysis of biocapped triangular cobalt cyclopentadienyl clusters, n (x = 0, 1, 5), containing mixed .pi.-acceptor X and .pi.-donor Y capping ligands : pronounced variations in redox behavior as a function of coordinating ligands", Journal of the American Chemical Society, 1986, 108, 5933. Purification of supporting electrolyte Tetra-n-butylammonium hexafluorophosphate (TBAPF6)
中文： A17196 Tetra-n-butylammonium hexafluorophosphate, 98% CAS 3109-63-5, 四正丁基六氟磷酸铵 , TBAPF6 是常用的支持电解质， Alfa 有 98% 的物质销售， 25g 400 元。据本实验室经验， Alfa 所售是有杂质的，对于高精度的电化学测量，比如说开孔富勒烯的 OSWV 测量是有影响的，这时需要对其进行纯化。 有两种纯化方法： 1 ） EtOH 和水重结晶。 2 ）无水 EtOH 乙醇重结晶三次，不过在我们实验室中发现重结晶一次足以应对我们的电化学实验室，条件为 25g TBAPF6100mL 乙醇 (EtOH) ，热溶，几乎全溶，自然冷却后冰箱冷冻 -16 度进一步析出，抽滤，真空干燥 24~72h, 收率 97% 。 参选文献 ： 1 ） Purification of Laboratory Chemicals (4th Edition) 2)Robert L. Bedard, Lawrence F. Dahl, "Electrochemical analysis of biocapped triangular cobalt cyclopentadienyl clusters, n (x = 0, 1, 5), containing mixed .pi.-acceptor X and .pi.-donor Y capping ligands : pronounced variations in redox behavior as a function of coordinating ligands", Journal of the American Chemical Society, 1986, 108, 5933. Purification of supporting electrolyte Tetra-n-butylammonium hexafluorophosphate (TBAPF6) English ： A17196 Tetra-n-butylammonium hexafluorophosphate (TBAPF6), 98%, CAS 3109-63-5,is common supporting electrolyte in electrochemistry test. Alfa corp sell it of 98% purity. According our lab’s experience, there was impurity in the raw commercial material, which meet rough electrochemistry rather than explicit test, e.g. OSWV of open-hole fullerene. We’d better to purify it by recrystalization. Two method: 1) recrystallization by ethanol and water. 2) recrystallization by absolute ethanol three times, however, recrystallization once is enough to common test. The recrystallization condition is : 25 g TBAPF6 was dissolved heatedly in 100mL EtOH, cooled down naturally , then cooled in fridg at -16 degree, filtered, dried in vacuo for 24~48h. Yield, 97%. References: 1 ） Purification of Laboratory Chemicals (4th Edition) 2)Robert L. Bedard, Lawrence F. Dahl, "Electrochemical analysis of biocapped triangular cobalt cyclopentadienyl clusters, n (x = 0, 1, 5), containing mixed .pi.-acceptor X and .pi.-donor Y capping ligands : pronounced variations in redox behavior as a function of coordinating ligands", Journal of the American Chemical Society, 1986, 108, 5933.
平时做CV和DPV经常用到支持电解质，如TBAPF6等，最近帮师弟做一个pH调控的实验，他给我的参考文献中没有用支持电解质， 而是用的背景电解质 NaCl,这两者有什么区别呢？ 支持电解质 http://goldbook.iupac.org/S06149.html supporting electrolyte An electrolyte solution, whose constituents are not electroactive in the range of applied potentials being studied, and whose ionic strength (and, therefore, contribution to the conductivity) is usually much larger than the concentration of an electroactive substance to be dissolved in it. 背景电解质 background electrolyte ground electrolyte http://www.qiji.cn/baike/Detailed/6162.html 指在极谱分析电解液中所加入的在一定电压范围内不在电极上起反应的过量电解质。主要为消除溶液中待测离子在电场作用下的迁移运动而产生的迁移电流，因为这部分电流不与被测物质的浓度成比例关系。其用量一般为被测物质浓度的50-100倍。选择这类物质的原则是：在溶液中有很好的导电性；与被测物质不发生作用；在被测物质处于还原（或氧化）电位时，不起电极反应。常用的有氯化钾、氯化铵、硝酸钾、盐酸、硫酸、氢氧化钠、醋酸钠、氢氧化铵等。 A. Turcanu, T. Bechtold / Dyes and Pigments 91 (2011) 324-331
Journal of Power Sources Article in Press, Accepted Manuscript - Note to users doi:10.1016/j.jpowsour.2011.02.060 | How to Cite or Link Using DOI Copyright 2011 Published by Elsevier B.V. Permissions Reprints Investigation of the Rechargeability of Li-O2 Batteries in Non-Aqueous Electrolyte Jie Xiao , a , , Jianzhi Hu a , Deyu Wang a , Dehong Hu a , Wu Xu a , Gordon L. Graff a , Zimin Nie a , Jun Liu a and Ji-Guang Zhang 1 , a , a Pacific Northwest National Laboratory, Energy and Environment Directorate, Richland, Washington 99352, USA Received 21 December 2010; accepted 18 February 2011. Available online 26 February 2011. Abstract To understand the limited cycle life performance and poor energy efficiency associated with rechargeable lithium-oxygen (Li-O2) batteries, the discharge products of primary Li-O2 cells at different depths of discharge (DOD) were systematically analyzed using XRD, FTIR and Ultra-high field MAS NMR. When discharged to 2.0V, the reaction products of Li-O2 cells include a small amount of Li2O2 along with Li2CO3 and RO-(C=O)-OLi) in the alkyl carbonate-based electrolyte. However, regardless of the DOD, there is no Li2O detected in the discharge products in the alkyl-carbonate electrolyte. For the first time it was revealed that in an oxygen atmosphere the high surface area carbon significantly reduces the electrochemical operation window of the electrolyte, and leads to plating of insoluble Li salts on the electrode at the end of the charging process. Therefore, the impedance of the Li-O2 cell continues to increase after each discharge and recharge process. After only a few cycles, the carbon air electrode is completely insulated by the accumulated Li salt terminating the cycling. Keywords: Li-air batteries; carbon air electrode; oxygen diffusion; energy storage
Journal of Power Sources Article in Press, Accepted Manuscript - Note to users doi:10.1016/j.jpowsour.2011.02.071 | How to Cite or Link Using DOI Copyright 2011 Published by Elsevier B.V. Permissions Reprints The effect of alkalinity and temperature on the performance of lithium-air fuel cell with hybrid electrolytes Ping He a , Yonggang Wang a and Haoshen Zhou , a , a Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Umezono 1-1-1, Tsukuba, 305-8568, Japan Received 27 October 2010; revised 21 February 2011; accepted 22 February 2011. Available online 26 February 2011. Abstract A lithium-air fuel cell combined an air cathode in aqueous electrolyte with a metallic lithium anode in organic electrolyte can continuously reduce O2 to provide capacity. Herein, the performance of this hybrid electrolyte based lithium-air fuel cell under the mixed control of alkalinity and temperature have been investigated by means of galvanistatic measurement and the analysis of electrochemical impedance spectra. Electromotive force and inner resistance of the cell decrease with the increase of LiOH concentration in aqueous electrolyte. The values ranged from 0.5 to 1.0M could be the suitable parameters for the LiOH concentration of aqueous electrolyte. Environment temperature exhibited a significant influence on the performance of lithium-air fuel cell. The Lithium-air fuel cell can provide a larger power at elevated temperature due to the decrease of all resistance of elements. Keywords: Lithium-air fuel cell; Lithium super ionic conductor glass; Electrochemical performance; Galvanistatic measurement; Electrochemical impedance spectra.
Journal of Power Sources Article in Press, Accepted Manuscript - Note to users doi:10.1016/j.jpowsour.2011.01.099 | How to Cite or Link Using DOI Copyright 2011 Published by Elsevier B.V. Permissions Reprints Controlling gas diffusion layer oxidation by homogeneous hydrophobic coating for polymer electrolyte fuel cells Yusuke Hiramitsu , a , , Hitoshi Sato a , , Kenji Kobayashi a , and Michio Hori a , a Fuel Cell Research Center, Daido University, 10-3 Takiharu-cho, Minami-ku, Nagoya 457-8530, Japan Received 21 June 2010; revised 10 January 2011; accepted 31 January 2011. Available online 17 February 2011. Abstract Reduced production costs and enhanced durability are necessary for practical application of polymer electrolyte fuel cells. There has been a great deal of concern about degradation of the gas diffusion layer located outside the membrane electrode assembly. However, very few studies have been carried out on the degradation process, and no suitable methods for improving the durability of the cell have been found. In this work, the influence on the cell performance and factors involved in the degradation of the gas diffusion layer has been clarified through power generation tests. Long-term power generation tests on single cells for 6000h were carried out under high humidity conditions with homogeneous and inhomogeneous hydrophobic coating gas diffusion layers. The results showed that the increase in the diffusion overvoltage from the gas diffusion layer could be controlled by the use of a homogeneous coating. Post analyses indicated that this occurred by controlling oxidation of the carbon fiber. Keywords: Polymer electrolyte fuel cell (PEFC); Water management; Water flooding; Gas diffusion layer (GDL); Durability; Long-term performance
Journal of Power Sources Article in Press, Accepted Manuscript - Note to users doi:10.1016/j.jpowsour.2011.02.023 | How to Cite or Link Using DOI Copyright 2011 Published by Elsevier B.V. Permissions Reprints A Study on lithium/air secondary batteries -Stability of the NASICON-type lithium ion conducting solid electrolyte in alkaline aqueous solutions Yuta Shimonishi a , Tao Zhang a , Nobuyuki Imanishi a , , , Dongmin Im b , Dong Joon Lee b , Atsushi Hirano a , Yasuo Takeda a , Osamu Yamamoto a and Nigel Sammes c a Department of Chemistry, Faculty of Engineering, Mie University, 1577 Kurimamachia-cho, Tsu, 514-8507, Japan b Emerging Technology Research Center, Samsung Advanced Institute of Technology, Samsung Electronics Co., Ltd., Yongin-si, 446-712, Korea c Department Metallurgical and Material Engineering, Colorado School of Mines, Golden, Colorado 80401, USA Received 28 December 2010; accepted 7 February 2011. Available online 12 February 2011. Abstract The stability of the high lithium ion conducting glass ceramics, Li1+x+yTi2-xAlxSiyP3-yO12 (LTAP) in alkaline aqueous solutions with and without LiCl has been examined. A significant conductivity decrease of the LTAP plate immersed in 0.057M LiOH aqueous solution at 50°C for 3 weeks was observed. However, no conductivity change of the LTAP plate immersed in LiCl saturated LiOH aqueous solutions at 50°C for 3 weeks was observed. The pH value of the LiCl-LiOH-H2O solution with saturated LiCl was in a range of 7 to 9. The molarity of LiOH and LiCl in the LiOH and LiCl saturated aqueous solution were estimated to be 5.12M and 11.57M, respectively, by analysis of Li+ and OH-. The high concentration of LiOH and the low pH value of 8.14 in this solution suggested that the dissociation of LiOH into Li+ and OH- is too low in the solution with a high concentration of Li+. These results suggest that the water stable LTAP could be used as a protect layer of the lithium metal anode in the lithium/air cell with LiCl saturated aqueous solution as the electrolyte, because the content of OH- ions in the LiCl saturated aqueous solution does not increase via the cell reaction of Li+1/2O2+H2O → 2LiOH, and LTAP is stable under a deep discharge state. Keywords: lithium/air battery; solid electrolyte; anode; alkaline solution
Journal of Power Sources Article in Press, Accepted Manuscript - Note to users doi:10.1016/j.jpowsour.2011.01.086 | How to Cite or Link Using DOI Copyright 2011 Published by Elsevier B.V. Permissions Reprints In-Situ Metal Ion Contamination and the Effects on PEM Fuel Cell Performance Mark Sulek , a , , Jim Adams a , Steve Kaberline a , Mark Ricketts a and James R. Waldecker a a Ford Motor Company, Research and Advanced Engineering, 2101 Village Road, Dearborn, MI 48121 Received 3 December 2010; revised 21 January 2011; accepted 27 January 2011. Available online 2 February 2011. Abstract Automotive fuel cell technology has made considerable progress, and hydrogen fuel cell vehicles are regarded as a possible long-term solution to reduce carbon dioxide emissions, reduce fossil fuel dependency and increase energy efficiency. Even though great strides have been made, durability is still an issue. One key challenge is controlling MEA contamination. Metal ion contamination within the membrane and the effects on fuel cell performance were investigated. Given the possible benefits of using stainless steel or aluminum for balance-of-plant components or bipolar plates, cations of Al, Fe, Ni and Cr were studied. Membranes were immersed in metal sulfide solutions of varying concentration and then assembled into fuel cell MEAs tested in-situ. The ranking of the four transition metals tested in terms of the greatest reduction in fuel cell performance was: Al3+ Fe2+Ni2+, Cr3+. For iron-contaminated membranes, no change in cell performance was detected until the membrane conductivity loss was greater than approximately 15%. Keywords: PEM fuel cells; metal contamination; membrane degradation; metal ions; membrane contamination
Journal of Power Sources Article in Press, Accepted Manuscript - Note to users doi:10.1016/j.jpowsour.2011.01.093 | How to Cite or Link Using DOI Copyright 2011 Published by Elsevier B.V. Permissions Reprints Lithium/Water Battery with Lithium Ion Conducting Glass-ceramic Electrolyte Takashi Katoh a , , , Yasushi Inda a , Kousuke Nakajima a , Rongbin Ye b and Mamoru Baba b a Ohara Inc., 1-15-30 Oyama, Chuo-ku, Sagamihara-shi, Kanagawa 252-5286, Japan b Faculty of Engineering, Iwate University, 4-3-5 Ueda, Morioka 020-8551, Japan Received 28 October 2010; revised 24 December 2010; accepted 24 January 2011. Available online 2 February 2011. Abstract Lithium/water batteries have attracted considerable attention as high power supply devices because they use high energy density lithium metal as an anode and water as a cathode. In this study, we investigate the use of lithium/water batteries that use a glass-ceramic plate as an electrolyte. Author Keywords: hsp sp="0.25"/°C temperature range.
口述形式 随想随写 锂空气电池的发展现在应该是进入了一个群雄并起的时段了 所以我们要思索的是： 1、锂空电池原理； 2、模块组成及其相应挖掘空间； 3、新型结构及原创想法的思索来源机理； 4、其他化学电源 的 并行借鉴发展。 *锂空气不外乎由氧还原催化剂、碳基正极载体材料、隔膜、电解质或电解液组成，那么需要的是 高级电催化机理相关知识、碳基材料的合成和认识基础和电解系列有机知识了； *但是现阶段最可能新潜力的新型电池结构的开发，当然还有新结构（包括1、电解质组态——是否也是聚合物复合隔膜处理，或是常规膜和电解液及其添加剂问题了；2、电极结构上的改进——使之更透气、更使得氧化还原的持续——碳和催化剂的分布复合问题——使得保证反应的不中止）那么以后我想，在材料方面就是这面最有得可为了——如何实现有效的分布和复合了； *——其实大家都知道的成功案例就是日本的王永刚（复旦夏永姚老师的博士）做的水系和有机系的复合电池——严格来说不是锂空气电池了：一边不变，另一边变得还算不错的文章哗啦啦的出来——但是给我们的启示应该是去寻找两端正负极的材料构成的思路—— 正负极要再元素周期表的左右两侧寻求最合适的反应元素——如果H能进来（其实就是燃料电池的模型了），那当然能量比是绝高的了，再者前些阵子的NaS，LiS，Mg空气电池其实就是为我们选择元素做了方向指示。。。 *当然这边不得不说的是，JACS新出来的贵金属PtAu复合的协同效应催化剂也是给我们指了条方向思路——复合负载——分布又兼起效。。。 *还有一个就是，参照传统锂电池发展的模式或有些粗略的启示：是否如新近的NL上的文章有机物直接负载在活性物质上呢？——那么也就是说如果将正极的复合材料在多孔或其他材料上直接复合处理成聚合物电解质在一起，可保证反应的路径效率以及循环倍率效率呢。。。 *胡言一句 多学科的交叉融合 将成就你我这一批人 在新兴方向的 。。。 本弱弱的博客将持续记录原创心得体会——主要方面在 成型商品电池（18650为主）的设计，传统锂电负极的构想研究，行业需求关于我们同行将来出路规划 三方面展开胡言乱语 以供彼此交流。 附注：（from http://en.wikipedia.org/wiki/Lithium_air_battery 维基百科） A lithium-air battery is a battery in which a lithium anode is electrochemically coupled to atmospheric oxygen through an air cathode . During discharge, lithium cations flow from the anode through an electrolyte and combine with oxygen at the cathode (typically consisting of porous carbon ) to form lithium oxide Li 2 O or lithium peroxide Li 2 O 2 which is inserted in the cathode; this is coupled to the flow of electrons from the battery's anode to the cathode through a load circuit. Lithium air batteries have higher energy density than lithium ion batteries because of the lighter cathode and the fact that oxygen is freely available in the environment and does not need to be stored in the battery. Theoretically, with oxygen as an unlimited cathode reactant, the capacity of the battery is limited by the Li anode. Lithium air batteries are currently under development and are not yet commercially available. 欢迎留言交流 放假回家 新年快乐哈
Journal of Power Sources Article in Press, Accepted Manuscript - Note to users doi:10.1016/j.jpowsour.2011.01.068 | How to Cite or Link Using DOI Copyright 2011 Published by Elsevier B.V. Permissions Reprints Thermal stability and flammability of electrolytes for lithium-ion batteries Catia Arbizzani a , Giulio Gabrielli a and Marina Mastragostino , a , a University of Bologna, Department of Metal Science, Electrochemistry and Chemical Techniques, Via San Donato 15, 40127 Bologna, Italy Received 11 October 2010; revised 7 December 2010; accepted 17 January 2011. Available online 26 January 2011. Abstract Safety is the key-feature of large-size lithium-ion batteries and thermal stability of the electrolytes is crucial. We investigated the thermal and flammability properties of mixed electrolytes based on the conventional ethylencarbonate-dimethylcarbonate (1:1wt/wt) - 1M LiPF6 and the hydrophobic ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI). The results of thermogravimetric analyses and flammability tests of mixed electrolytes of different composition are reported and discussed. An important finding is that though the mixtures with high contents of ionic liquid are more difficult to ignite, they burn for a longer time, once they are ignited. Keywords: flammability test; ionic liquid; lithium-ion battery; safety; thermal stability
标签: 电解质
