JoVE Journal > Engineering
Summary
Abstract
Introduction
Protocol
Risultati
Discussion
Divulgazioni
Acknowledgements
Materials
Riferimenti
Traduzione automatica
Please note that all translations are automatically generated. Click here for the English version.
Ingegneria

电化学测试的协议及表征非质子锂的O<sub> 2</sub>电池

Published: July 12, 2016
doi:
10.3791/53740
, , ,
1Chemistry Sciences and Engineering Division,Argonne National Laboratory, 2X-ray Science Division, Advanced Photon Sources,Argonne National Laboratory

Summary

A protocol for the electrochemical testing of an aprotic Li-O2 battery with the preparation of electrodes and electrolytes and an introduction of the frequently used methods of characterization is presented here.

Abstract

We demonstrate a method for electrochemical testing of an aprotic Li-O2 battery. An aprotic Li-O2 battery is made of a Li-metal anode, an aprotic electrolyte, and an O2-breathing cathode. The aprotic electrolyte is a solution of lithium salt with aprotic solvent; and porous carbon is commonly used as the cathode substrate. To improve the performance, an electrocatalyst is deposited onto the porous carbon substrate by certain deposition methods, such as atomic layer deposition (ALD) and wet-chemistry reaction. The as-prepared cathode materials are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray absorption near edge structure (XANES). A Swagelok-type cell, sealed in a glass chamber filled with pure O2, is used for the electrochemical test on a battery test system. The cells are tested under either capacity-controlled mode or voltage controlled mode. The reaction products are investigated by electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and Raman spectroscopy to study the possible pathway of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). This protocol demonstrates a systematic and efficient arrangement of routine tests of the aprotic Li-O2 battery, including the electrochemical test and characterization of battery materials.

Introduction

1996年，亚伯拉罕和江1报告的第一个可逆的非水性锂O 2的电池由多孔碳阴极，有机电解质和锂金属阳极。自那时以来，由于其极高的理论能量密度超过任何其他现有的能量存储系统中，锂O 2电池，其诱导在阳极上的电流流动通过锂的氧化和氧的在阴极的还原（整体反应力+ + O 2 + E – ↔李2 O 2），最近收到显著的兴趣1-8。

下列要求的负极材料，将能够满足的李-O高性能需求2电池：（1）快速氧气扩散; （2）良好的电气和离子导电性; （3）高比表面积和（4）的稳定性。两个阴极的表面积和孔隙率的临界。李-O 2电池电化学性能9-12的多孔结构允许从锂阳离子与O 2反应产生的固体排放产品的沉积;和更大的表面积提供更多的活性位点，以适应电粒子加速电化学反应。例如电催化剂是由特定的沉积方法，其提供到基底和催化剂颗粒的良好控制附着力强，与基板的原始多孔表面结构的保存加到阴极材料13-17所制备的材料进行测试在世伟洛克型细胞作为非质子锂O 2电池的阴极。然而，电池的性能不仅取决于阴极材料的性质，而且还对非质子电解质18-22和锂金属阳极的类型。23-26更多影响包括的量和材料的浓度和p在充电/放电测试中使用rocedure。适当的条件和协议将优化和改进电池材料的整体性能。

除了 ​​电化学测试的结果，电池的性能还可以通过表征原始材料和反应产物进行评价。27-33扫描电子显微镜（SEM）被用来研究在阴极材料和形态的表面微观结构放电产物的演变。透射电子显微镜（TEM），X射线近边结构（XANES）吸收，和X射线光电子能谱（XPS）可以被用来确定超微结构，化学状态，和元件的组成部分，特别是对于那些催化剂纳米颗粒。高能量X射线衍射（XRD）用于直接识别该结晶放电产物。可能的电解质的分解可以通过衰减全反射傅立叶变换确定红外（ATR-FTIR）和拉曼光谱。

本文是演示的非质子锂O 2电池的常规试验，包括准备电池材料及配件，电化学性能测试和表征质朴的材料和反应产物的系统和有效的安排的协议。详细的视频协议是为了帮助在该领域从业者的新避免与李-O 2电池的性能测试和表征相关的许多常见的陷阱。

Protocol

使用前请咨询所有相关的材料安全数据表（MSDS）。几个在这些合成中使用的化学品是剧毒和致癌性。相比，他们的大部分对手纳米材料可能有额外的危害。进行纳米晶体的反应包括利用工程控制（通风橱，手套箱）和个人防护装备时，请使用所有适当安全守则（安全眼镜，手套，实验室外套，全长裤，封闭趾鞋）。以下过程部分涉及标准自由的空气处理技术。 1.正极材料的合…

Representative Results

图1a所示为锂O 2的电池测试的世伟洛克型格的设置。一块锂膜的阳极端被放置在一个不锈钢棒。多孔阴极通过铝管是开放的纯O 2。玻璃纤维被用作隔板和非质子电解质的吸收;和Al-网格被用作集电体。整个洛克型电池被密封在填充有超高纯度氧的玻璃室中。在深入研究中，多个表征方法被施加到检查的电池系统，包括所制备的电极材料和反应产…

Discussion

考虑锂的 O 2的电池系统的空气的敏感性，特别是CO 2和水分，大量的在协议的步骤，以减少干扰物和避免副反应是必要的。例如，洛克式电池在充满氩气与O 2的<0.5ppm的和H 2 O <0.5ppm的手套箱组装;和所有的阴极材料，电解质溶剂和盐，玻璃纤维，洛克的部件，在玻璃室组装前干燥以减少水分污染。阳极端是一个不锈钢棒，以避免锂金属和O 2之间?…

Divulgazioni

The authors have nothing to disclose.

Acknowledgements

Research at Argonne National Laboratory was funded by U.S. Department of Energy, FreedomCAR and Vehicle Technologies Office. Use of the Advanced Photon Source and research carried out in the Electron Microscopy Center at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

Materials

1-Methyl-2-pyrrolidinone (NMP), 99.5% Sigma-Aldrich 328634
Battery test system MACCOR Series 4000 Automated Test System
Dimethyl carbonate (DMC), ≥99% Sigma-Aldrich 517127
Ethyl alcohol, ≥99.5% Sigma-Aldrich 459844
Formaldehyde solution, 37 wt. % in H2O Sigma-Aldrich 252549
Graphitized Carbon black, >99.95% Sigma-Aldrich 699632
Iron(III) chloride (FeCl3), 97% Sigma-Aldrich 157740
Kapton polyimide tubing Cole-Parmer EW-95820-09
Kapton polymide tape Cole-Parmer EW-08277-80
Kapton window film SPEX Sample Prep 3511
Lithium Chip (99.9% Lithium) MTI Corporation EQ-Lib-LiC25
Lithium trifluoromethanesulfonate (LiCF3SO3) Sigma-Aldrich 481548
Palladium hexafluoroacetylacetonate (Pd(hfac)2), 99.9% Aldrich 401471
Poly(vinylidene fluoride) (PVDF) Aldrich 182702
Potassium permanganate (KMnO4), ≥99.0%  Sigma-Aldrich 223468
Sodium hydroxide (NaOH), ≥97.0% Sigma-Aldrich 221465
Tetraethylene glycol dimethyl ether (TEGDME), ≥99% Aldrich 172405
Toray 030 carbon paper ElectroChem Inc. 590637
DOWNLOAD MATERIALS LIST

Riferimenti

  1. Abraham, K. M., Jiang, Z. A polymer electrolyte-based rechargeable lithium/oxygen battery. J. Electrochem. Soc. 143, 1-5 (1996).
  2. Bruce, P. G., Freunberger, S. A., Hardwick, L. J., Tarascon, J. -. M. Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 11, 19-29 (2012).
  3. Lu, J., et al. Aprotic and Aqueous Li-O2 Batteries. Chem. Rev. 114, 5611-5640 (2014).
  4. Black, R., Adams, B., Nazar, L. F. Non-Aqueous and Hybrid Li-O2 Batteries. Adv. Energy Mater. 2, 801-815 (2012).
  5. Bruce, P. G., Hardwick, L. J., Abraham, K. M. Lithium-air and lithium-sulfur batteries. MRS Bull. 36, 506-512 (2011).
  6. Christensen, J., et al. A Critical Review of Li/Air Batteries. J. Electrochem. Soc. 159, 1-30 (2012).
  7. Girishkumar, G., McCloskey, B., Luntz, A. C., Swanson, S., Wilcke, W. Lithium-Air Battery: Promise and Challenges. J. Phys. Chem. Lett. 1, 2193-2203 (2010).
  8. Lu, J., Amine, K. Recent Research Progress on Non-aqueous Lithium-Air Batteries from Argonne National Laboratory. Energies. 6, 6016-6044 (2013).
  9. Ding, N., et al. Influence of carbon pore size on the discharge capacity of Li-O2 batteries. J. Mater. Chem. A. 2, 12433 (2014).
  10. Nimon, V. Y., Visco, S. J., De Jonghe, L. C., Volfkovich, Y. M., Bograchev, D. A. Modeling and Experimental Study of Porous Carbon Cathodes in Li-O2 Cells with Non-Aqueous Electrolyte. ECS Electrochem. Lett. 2, 33-35 (2013).
  11. Ottakam Thotiyl, M. M., Freunberger, S. A., Peng, Z., Bruce, P. G. The Carbon Electrode in Nonaqueous Li-O2 Cells. J. Am. Chem. Soc. 135, 494-500 (2012).
  12. Park, J. -. B., Lee, J., Yoon, C. S., Sun, Y. -. K. Ordered Mesoporous Carbon Electrodes for Li-O2 Batteries. Acs Appl. Mater. Interfaces. 5, 13426-13431 (2013).
  13. Lei, Y., et al. Synthesis of porous carbon supported palladium nanoparticle catalysts by atomic layer deposition: application for rechargeable lithium-O2 battery. Nano Lett. 13, 4182-4189 (2013).
  14. Lu, J., et al. Effect of the size-selective silver clusters on lithium peroxide morphology in lithium-oxygen batteries. Nat. Commun. 5, 4895 (2014).
  15. Lu, J., et al. A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries. Nat. Commun. 4, 2383 (2013).
  16. Lu, J., et al. Synthesis and characterization of uniformly dispersed Fe3O4/Fe nanocomposite on porous carbon: application for rechargeable Li-O2 batteries. RSC Adv. 3, 8276-8285 (2013).
  17. Luo, X., et al. Pd nanoparticles on ZnO-passivated porous carbon by atomic layer deposition: an effective electrochemical catalyst for Li-O2 battery. Nanotechnology. 26, 164003 (2015).
  18. Freunberger, S. A., et al. The Lithium-Oxygen Battery with Ether-Based Electrolytes. Angew. Chem. Int. Ed. 50, 8609-8613 (2011).
  19. Laoire, C. O., Mukerjee, S., Abraham, K. M., Plichta, E. J., Hendrickson, M. A. Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium-Air Battery. J. Phys. Chem. C. 114, 9178-9186 (2010).
  20. McCloskey, B. D., Bethune, D. S., Shelby, R. M., Girishkumar, G., Luntz, A. C. Solvents’ Critical Rope in Nonaqueous Lithium-Oxygen Battery Electrochemistry. J. Phys. Chem. Lett. 2, 1161-1166 (2011).
  21. Assary, R. S., et al. Molecular-Level Insights into the Reactivity of Siloxane-Based Electrolytes at a Lithium-Metal Anode. ChemPhysChem. 15, 2077-2083 (2014).
  22. Du, P., et al. Compatibility of lithium salts with solvent of the non-aqueous electrolyte in Li-O2 batteries. Phys. Chem. Chem. Phys. 15, 5572-5581 (2013).
  23. Aleshin, G. Y., et al. Protected anodes for lithium-air batteries. Solid State Ion. 184, 62-64 (2011).
  24. Assary, R. S., et al. The Effect of Oxygen Crossover on the Anode of a Li-O2 Battery using an Ether-Based Solvent: Insights from Experimental and Computational Studies. ChemSusChem. 6, 51-55 (2013).
  25. Aurbach, D., Zinigrad, E., Cohen, Y., Teller, H. A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ion. 148, 405-416 (2002).
  26. Dey, A. N. Lithium Anode Film And Organic And Inorganic Electrolyte Batteries. Thin Solid Films. 43, 131-171 (1977).
  27. Lau, K. C., Lu, J., Luo, X., Curtiss, L. A., Amine, K. Implications of the Unpaired Spins in Li-O2 Battery Chemistry and Electrochemistry: A Minireview. ChemPlusChem. 80, 336-343 (2015).
  28. Lau, K. C., et al. Theoretical Exploration of Various Lithium Peroxide Crystal Structures in a Li-Air Battery. Energies. 8, 529-548 (2015).
  29. Black, R., et al. Screening for Superoxide Reactivity in Li-O2 Batteries: Effect on Li2O2/LiOH Crystallization. J. Am. Chem. Soc. 134, 2902-2905 (2012).
  30. Gallant, B. M., et al. Influence of Li2O2 morphology on oxygen reduction and evolution kinetics in Li-O2 batteries. Energy Environ. Sci. 6, 2518-2528 (2013).
  31. Lu, J., et al. Magnetism in Lithium-Oxygen Discharge Product. ChemSusChem. 6, 1196-1202 (2013).
  32. Xu, J. -. J., Wang, Z. -. L., Xu, D., Zhang, L. -. L., Zhang, X. -. B. Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries. Nat. Commun. 4, 2438 (2013).
  33. Zhong, L., et al. In Situ Transmission Electron Microscopy Observations of Electrochemical Oxidation of Li2O2. Nano Lett. 13, 2209-2214 (2013).
  34. . . Hitachi S-4700 SEM Training & Reference Guide. , (2015).
  35. . . SEM Hitachi S4700 User Manual. , (2015).
  36. Goldstein, J., et al. . Scanning Electron Microscopy and X-ray Microanalysis. , (2003).
  37. . X-Ray Photoelectron Spectrometer Operation Procedure Available from: https://nanofabrication.4dlabs.ca (2015)
  38. Haasch, R. T., Sardela, M. . Practical Materials Characterization. , 93-132 (2014).
  39. . . JEM-2100F Field Emission Transmission Electron Microscope. , (2015).
  40. Wen, J. -. G., Sardela, M. . Practical Materials Characterization. , 189-229 (2014).
  41. Williams, D. B., Carter, C. B. . Transmission Electron Microscopy. , (2009).
  42. . . Beamline 11-ID-C: High-energy Diffraction Beamline. , (2015).
  43. . . Beamline 11-ID-D: Sector 11 – Time Resolved X-ray Spectroscopy and Scattering. , (2015).
  44. Sardela, M. R., Sardela, M. . Practical Materials Characterization. , 1-41 (2014).
  45. . . Beamline 9-BM-B,C: X-ray Absorption Spectroscopy Beamline. , (2015).
  46. . . Beamline 20-BM-B: X-ray Absorption Spectroscopy Beamline. , (2015).
  47. Bunker, G. . Introduction to XAFS: A Practical Guide to X-ray Absorption Fine Structure Spectroscopy. , (2010).
  48. . . Nicolet FT-IR User’s Guide. , (2015).
  49. . . Nicolet iS5 User Guide. , (2015).
  50. . . Renishaw inVia Raman Microscope Training Notebook. , (2015).
  51. . . Renishaw InVia Quick Operation Summary. , (2015).
  52. Mitchell, R. R., Gallant, B. M., Thompson, C. V., Shao-Horn, Y. All-carbon-nanofiber electrodes for high-energy rechargeable Li-O2 batteries. Energy Environ. Sci. 4, 2952-2958 (2011).

Tags

Li-O2 BatteryAprotic ElectrolyteCathode MaterialAnodeSwagelok CellOxygenElectrochemical CharacterizationProtocolLithium TriflateTetraethylene Glycol Dimethyl EtherPVDFCarbon Paper
check_url/it/53740?article_type=t

Play Video
PDF
DOI
DOWNLOAD MATERIALS LIST
Citazione di questo articolo
Luo, X., Wu, T., Lu, J., Amine, K. Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery. J. Vis. Exp. (113), e53740, doi:10.3791/53740 (2016).
Scarica citazione
Ristampe e autorizzazioni

View Video

✖

To prove you're not a robot, please enter the text in the image below

CAPTCHA Image
Play CAPTCHA Audio
Refresh Image