Skip to main content
SpringerLink
Log in

Designer Interphases for the Lithium-Oxygen Electrochemical Cell

  • Chapter
  • First Online:
Rational Design of Nanostructured Polymer Electrolytes and Solid–Liquid Interphases for Lithium Batteries

Part of the book series: Springer Theses ((Springer Theses))

  • 774 Accesses

Abstract

An electrochemical cell based on the reversible oxygen reduction reaction (ORR), 2Li+ + 2e− + O2 ↔ Li2O2, provides among the most energy dense platform for portable electrical energy storage. Such lithium-oxygen (Li-O2) cells offer theoretical specific energies competitive with fossil fuels and have long been considered an important storage technology for enabling electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these fundamental problems lead to practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in situ formation of solid electrolyte interphases (SEIs) based on bromide ionomers tethered to the Li anode that take advantage of three powerful, fundamental processes for overcoming the most stubborn of these challenges. Formed in situ, the ionomer SEIs are specifically shown to exhibit three attributes required for stable Li-O2 cell operation. First, they protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Second, bromine species liberated during the anchoring reaction function as a redox mediator for the recharge reaction at the cathode, reducing the charge overpotential. Finally, the ionomer SEI form an exceptionally stable interphase with Li, which is shown to protect the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates but are known for their reactivity with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a highly promising materials platform for addressing the major barriers to practical Li-O2 storage technology.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 129.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. 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)

    Article  CAS  Google Scholar 

  2. Luntz, A.C., McCloskey, B.D.: Nonaqueous Li-air batteries: a status report. Chem. Rev. 114, 11721–11750 (2014)

    Article  CAS  Google Scholar 

  3. 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)

    Article  CAS  Google Scholar 

  4. Aurbach, D., McCloskey, B.D., Nazar, L.F., Bruce, P.G.: Advances in understanding mechanisms underpinning lithium–air batteries. Nat. Energy. 1, 16128 (2016)

    Article  CAS  Google Scholar 

  5. Lu, Y.-C., Gasteiger, H.A., Parent, M.C., Chiloyan, V., Shao-Horn, Y.: The influence of catalysts on discharge and charge voltages of rechargeable Li–oxygen batteries. Electrochem. Solid-State Lett. 13, A69 (2010)

    Article  CAS  Google Scholar 

  6. Mccloskey, B.D., et al.: Combining accurate O2 and Li2O2 assays to separate discharge and charge stability limitations in nonaqueous Li-O2 batteries. J. Phys. Chem. Lett. 4, 2989–2993 (2013)

    Article  CAS  Google Scholar 

  7. McCloskey, B.D., et al.: Limitations in rechargeability of Li-O2 batteries and possible origins. J. Phys. Chem. Lett. 3, 3043–3047 (2012)

    Article  CAS  Google Scholar 

  8. McCloskey, B.D., et al.: Twin problems of interfacial carbonate formation in nonaqueous Li-O2 batteries. J. Phys. Chem. Lett. 3, 997–1001 (2012)

    Article  CAS  Google Scholar 

  9. Ottakam Thotiyl, M.M., et al.: A stable cathode for the aprotic Li-O2 battery. Nat. Mater. 12, 1050–1056 (2013)

    Article  CAS  Google Scholar 

  10. Lau, S., Archer, L.A.: Nucleation and growth of lithium peroxide in the Li-O2 battery. Nano Lett. 15, 5995–6002 (2015)

    Article  CAS  Google Scholar 

  11. Højberg, J., et al.: An electrochemical impedance spectroscopy investigation of the overpotentials in Li-O2 batteries. ACS Appl. Mater. Interfaces. 7, 4039–4047 (2015)

    Article  Google Scholar 

  12. Chen, Y., Freunberger, S.A., Peng, Z., Fontaine, O., Bruce, P.G.: Charging a Li-O2 battery using a redox mediator. Nat. Chem. 5, 489–494 (2013)

    Article  Google Scholar 

  13. Lee, D.J., Lee, H., Kim, Y.J., Park, J.K., Kim, H.T.: Sustainable redox mediation for lithium-oxygen batteries by a composite protective layer on the lithium-metal anode. Adv. Mater. 28, 857–863 (2016)

    Article  CAS  Google Scholar 

  14. Bergner, B.J., et al.: Understanding the fundamentals of redox mediators in Li-O2 batteries: a case study on nitroxides. Phys. Chem. Chem. Phys. 17, 31769–31779 (2015)

    Article  Google Scholar 

  15. Liu, T., et al.: Cycling Li-O2 batteries via LiOH formation and decomposition. Science (80-. ). 350, 3–6 (2015)

    Google Scholar 

  16. Kwak, W.-J., et al.: Understanding the behavior of Li–oxygen cells containing LiI. J. Mater. Chem. A. 3, 8855–8864 (2015)

    Article  CAS  Google Scholar 

  17. Lim, H.D., et al.: Superior rechargeability and efficiency of lithium-oxygen batteries: hierarchical air electrode architecture combined with a soluble catalyst. Angew. Chem. Int. Ed. Engl. 53, 3926–3931 (2014)

    Article  CAS  Google Scholar 

  18. Kundu, D., Black, R., Adams, B., Nazar, L.F.: A highly active low voltage redox mediator for enhanced rechargeability of lithium-oxygen batteries. ACS Cent. Sci. 1, 510–515 (2015)

    Article  CAS  Google Scholar 

  19. Sun, D., et al.: A solution-phase bifunctional catalyst for lithium − oxygen batteries. J. Am. Chem. Soc. 136, 8941–8946 (2014)

    Article  CAS  Google Scholar 

  20. Hirshberg, D., et al.: Li-O2 cells with LiBr as an electrolyte and redox mediator. Energy Environ. Sci. 9, 2334–2345 (2016)

    Article  Google Scholar 

  21. Zhang, T., Liao, K., He, P., Zhou, H.: A self-defense redox mediator for efficient lithium-O2 batteries. Energy Environ. Sci. 9, 1024–1030 (2015)

    Article  Google Scholar 

  22. Veith, G.M., Nanda, J., Delmau, L.H., Dudney, N.J.: Influence of lithium salts on the discharge chemistry of Li − air cells. J. Phys. Chem. Lett. 3, 1242–1247 (2012)

    Article  CAS  Google Scholar 

  23. 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)

    Article  CAS  Google Scholar 

  24. Tikekar, M.D., Choudhury, S., Tu, Z., Archer, L.A.: Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy. 1, 16114 (2016)

    Article  CAS  Google Scholar 

  25. Freunberger, S.A., et al.: Reactions in the rechargeable lithium-O2 battery with alkyl carbonate electrolytes. J. Am. Chem. Soc. 133, 8040–8047 (2011)

    Article  CAS  Google Scholar 

  26. Bryantsev, V.S., et al.: The identification of stable solvents for nonaqueous rechargeable Li-air batteries. J. Electrochem. Soc. 160, A160–A171 (2012)

    Article  Google Scholar 

  27. Burke, C.M., Pande, V., Khetan, A., Viswanathan, V., Mccloskey, B.D.: Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li – O 2 battery capacity. Proc. Natl. Acad. Sci. 2, 201505728 (2015)

    Google Scholar 

  28. Johnson, L., et al.: The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li-O2 batteries. Nat. Chem. 6, 1091–1099 (2014)

    Article  CAS  Google Scholar 

  29. Khetan, A., Luntz, A., Viswanathan, V.: Trade-offs in capacity and rechargeability in nonaqueous Li-O2 batteries: solution-driven growth versus nucleophilic stability. J. Phys. Chem. Lett. 6, 1254–1259 (2015)

    Article  CAS  Google Scholar 

  30. Knudsen, K.B., Vegge, T., McCloskey, B.D., Hjelm, J.: An electrochemical impedance spectroscopy study on the effects of the surface- and solution-based mechanisms in Li-O2 cells. J. Electrochem. Soc. 163, A2065–A2071 (2016)

    Article  CAS  Google Scholar 

  31. Aetukuri, N.B., et al.: Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li–O2 batteries. Nat. Chem. 7, 50–56 (2015)

    Article  CAS  Google Scholar 

  32. Rosenman, A., et al.: The effect of interactions and reduction products of LiNO3, the anti-shuttle agent, in Li-S battery systems. J. Electrochem. Soc. 162, A470–A473 (2015)

    Article  CAS  Google Scholar 

  33. Zhang, S.S.: Role of LiNO3 in rechargeable lithium/sulfur battery. Electrochim. Acta. 70, 344–348 (2012)

    Article  CAS  Google Scholar 

  34. Liang, X., et al.: Improved cycling performances of lithium sulfur batteries with LiNO 3-modified electrolyte. J. Power Sources. 196, 9839–9843 (2011)

    Article  CAS  Google Scholar 

  35. Aurbach, D., et al.: On the surface chemical aspects of very high energy density, rechargeable Li–sulfur batteries. J. Electrochem. Soc. 156, A694–A702 (2009)

    Article  CAS  Google Scholar 

  36. Walker, W., et al.: A rechargeable Li-O-2 battery using a lithium nitrate/N, N-dimethylacetamide electrolyte. J. Am. Chem. Soc. 135, 2076–2079 (2013)

    Article  CAS  Google Scholar 

  37. Choudhury, S., Archer, L.A.: Lithium fluoride additives for stable cycling of lithium batteries at high current densities. Adv. Electron. Mater. 1–6 (2015). https://doi.org/10.1002/aelm.201500246

    Article  Google Scholar 

  38. Choudhury, S., Mangal, R., Agrawal, A., Archer, L.A.: A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles. Nat. Commun. 1–9 (2015). https://doi.org/10.1038/ncomms10101

  39. Agrawal, A., Choudhury, S., Archer, L.A.: A highly conductive, non-flammable polymer–nanoparticle hybrid electrolyte. RSC Adv. 5, 20800–20809 (2015)

    Article  CAS  Google Scholar 

  40. Tarascon, J.M., Armand, M.: Issues and challenges facing rechargeable lithium batteries. Nature. 414, 359–367 (2001)

    Article  CAS  Google Scholar 

  41. Kashiwagi, T., et al.: Nanoparticle networks reduce the flammability of polymer nanocomposites. Nat. Mater. 4, 928–933 (2005)

    Article  CAS  Google Scholar 

  42. Tu, Z., Nath, P., Lu, Y., Tikekar, M.D., Archer, L.A.: Nanostructured electrolytes for stable lithium electrodeposition in secondary batteries. Acc. Chem. Res. acs.accounts. 5b00427, (2015). https://doi.org/10.1021/acs.accounts.5b00427

    Article  CAS  Google Scholar 

  43. Cheng, X., et al.: A review of solid electrolyte interphases on lithium metal anode. Adv. Sci. 3, 1–20 (2016)

    CAS  Google Scholar 

  44. Tikekar, M.D., Archer, L.A., Koch, D.L.: Stability analysis of electrodeposition across a structured electrolyte with immobilized anions. J. Electrochem. Soc. 161, A847–A855 (2014)

    Article  CAS  Google Scholar 

  45. Tikekar, M.D., Archer, L.A., Koch, D.L.: Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions. Sci. Adv. 2, e1600320 (2016)

    Article  Google Scholar 

  46. Ozhabes, Y., Gunceler, D., Arias, T.A.: Stability and surface diffusion at lithium-electrolyte interphases with connections to dendrite suppression. arXiv. 1504.05799, 1–7 (2015)

    Google Scholar 

  47. Lu, Y., et al.: Stable cycling of lithium metal batteries using high transference number electrolytes. Adv. Energy Mater. 5, n/a–n/a (2015)

    Article  CAS  Google Scholar 

  48. Schaefer, J.L., Yanga, D.A., Archer, L.A.: High lithium transference number electrolytes via creation of 3-dimensional, charged, nanoporous networks from dense functionalized nanoparticle composites. Chem. Mater. 25, 834–839 (2013)

    Article  CAS  Google Scholar 

  49. Bouchet, R., et al.: Efficient electrolytes for lithium-metal batteries. Nat. Mater. 12, 452–457 (2013)

    Article  CAS  Google Scholar 

  50. Yao, K.P.C., et al.: Thermal stability of Li2O2 and Li2O for Li-air batteries: in situ XRD and XPS studies. J. Electrochem. Soc. 160, A824–A831 (2013)

    Article  CAS  Google Scholar 

  51. Lu, Y.-C., et al.: In situ ambient pressure X-ray photoelectron spectroscopy studies of lithium-oxygen redox reactions. Sci. Rep. 2, 715 (2012)

    Article  Google Scholar 

  52. Kundu, D., Black, R., Berg, E.J., Nazar, L.F.: A highly active nanostructured metallic oxide cathode for aprotic Li–O 2 batteries. Energy Environ. Sci. 8, 1292–1298 (2015)

    Article  CAS  Google Scholar 

  53. Moulder, J., Stickle, W., Sobol, P., Bomben, K.: Handbook of X-ray Photoelectron Spectroscopy. PerkinElmer Corp. Eden Prairie, Eden Prairie (1992)

    Google Scholar 

  54. Zhang, Z., et al.: Increased stability toward oxygen reduction products for lithium-air batteries with oligoether-functionalized silane electrolytes. J. Phys. Chem. C. 115, 25535–25542 (2011)

    Article  CAS  Google Scholar 

  55. Lu, J., et al.: Magnetism in lithium-oxygen discharge product. ChemSusChem. 6, 1196–1202 (2013)

    Article  CAS  Google Scholar 

  56. Basile, A., Bhatt, A.I., O’Mullane, A.P.: Stabilizing lithium metal using ionic liquids for long-lived batteries. Nat. Commun. 7, 1–11 (2016)

    Article  Google Scholar 

  57. Hausbrand, R., et al.: Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: methodology, insights and novel approaches. Mater. Sci. Eng. B. 192, 3–25 (2015)

    Article  CAS  Google Scholar 

  58. Xiong, S., Xie, K., Diao, Y., Hong, X.: Properties of surface film on lithium anode with LiNO 3 as lithium salt in electrolyte solution for lithium-sulfur batteries. Electrochim. Acta. 83, 78–86 (2012)

    Article  CAS  Google Scholar 

  59. Wu, Y., Fang, S., Jiang, Y.: Effects of nitrogen on the carbon anode of a lithium secondary battery. Sci. York. 120, 117–123 (1999)

    CAS  Google Scholar 

  60. NIST X-ray photoelectron spectroscopy database, Version 4.1. Natl. Inst. Stand. Technol. Gaithersbg. 1, (2012)

    Google Scholar 

  61. Ferrighi, L., et al.: Control of the intermolecular coupling of dibromotetracene on Cu(110) by the sequential activation of C-Br and C-H bonds. Chem. Eur. J. 21, 5826–5834 (2015)

    Article  CAS  Google Scholar 

  62. Basagni, A., et al.: On-surface photo-dissociation of C–Br bonds: towards room temperature Ullmann coupling. Chem. Commun. 51, 12593–12596 (2015)

    Article  CAS  Google Scholar 

  63. Gutzler, R., et al.: Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver. Nanoscale. 6, 2660–2668 (2014)

    Article  CAS  Google Scholar 

  64. Desai, S.M., Solanky, S.S., Mandale, A.B., Rathore, K., Singh, R.P.: Controlled grafting of N-isoproply acrylamide brushes onto self-standing isotactic polypropylene thin films: surface initiated atom transfer radical polymerization. Polymer. 44, 7645–7649 (2003)

    Article  CAS  Google Scholar 

  65. Di Giovannantonio, M., et al.: Insight into organometallic intermediate and its evolution to covalent bonding in surface-confined ullmann polymerization. ACS Nano. 7, 8190–8198 (2013)

    Article  Google Scholar 

  66. Jäckle, M., Groß, A.: Microscopic properties of lithium, sodium, and magnesium battery anode materials related to possible dendrite growth. J. Chem. Phys. 141, 174710 (2014)

    Article  Google Scholar 

  67. Ha, S., et al.: Magnesium ( II ) Bis (trifluoromethane sulfonyl) Imide-based electrolytes with wide electrochemical windows for rechargeable magnesium batteries. ACS Appl. Mater. Interfaces. 6, 4063–4073 (2014)

    Article  CAS  Google Scholar 

  68. Feng, S., et al.: Single lithium-ion conducting polymer electrolytes based on poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide] anions. Electrochim. Acta. 93, 254–263 (2013)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Snehashis Choudhury

Authors
  1. Snehashis Choudhury
    View author publications

    You can also search for this author in PubMed Google Scholar

Appendix: Supplementary Information

Appendix: Supplementary Information

Supplementary Fig. 8.1
figure 5

2D EDAX mapping of lithium-deposited stainless steel substrate with 1 M LiNO3-DMAc electrolyte and 10% ionomer additive. The atoms taken into consideration are sulfur, bromine, carbon, oxygen, and nitrogen

Full size image
Supplementary Fig. 8.2
figure 6

XPS results showing the binding energy of Li and O atom with control electrolyte of 1 M LiNO3-DMAc electrolyte. The first row shows results when the battery is discharged to 2 V; the second row shows results when the Li-O2 battery is cycled once for 1 h

Full size image
Supplementary Fig. 8.3
figure 7

Nyquist plots of 1 M LiNO3-DMAc enriched with 5% (by wt.) of ionomer additive, showing impedance for different storage times of the battery

Full size image
Supplementary Fig. 8.4
figure 8

Equivalent circuit model to fit the Nyquist plot obtained from impedance spectroscopy measurement comprising of bulk resistance, interfacial resistance parallel to a constant phase element, and a solid-state diffusion element

Full size image
Supplementary Fig. 8.5
figure 9

Nyquist plots showing experimental as well as circuit model fitted results of impedance measurements with symmetric cells for control electrolyte and ionomer-added batteries after 48 hrs and 56 hrs of storage. The red plot represents control and black shows data for ionomer-added electrolyte

Full size image
Supplementary Fig. 8.6
figure 10

Stripping and plating of Li vs. SS cell after depositing 10 mAh/cm2 of lithium onto stainless steel. It is seen that for all cells the voltage diverges for all cells however at different point of times

Full size image
Supplementary Fig. 8.7
figure 11

Size analysis of lithium peroxide particles after discharging a Li-O2 cell with 1 M LiNO3-DMAc electrolyte and ionomer additive at different current densities as indicated in the box

Full size image
Supplementary Table 8.1 Atomic percentage of detected elements on lithium anodes
Full size table

8.1.1 Experimental

8.1.1.1 Li-O2 Battery Methods and Materials

8.1.1.1.1 Cathode Preparation

A cathode slurry was prepared by mixing 180 mg of Super P carbon (TIMCAL), 20 mg of polyvinylidene fluoride (PVDF; Aldrich), and 2000 mg of N-Methyl-2-pyrrolidone (NMP; Aldrich) in a ball mill at 50 Hz for 1 h. Toray TGP-H-030 carbon paper was coated with an 80 μm thick layer of carbon slurry using a doctor blade. The resulting coated carbon paper was dried at 100 °C overnight under vacuum and transferred into an argon-filled glovebox (O2 < 0.2 ppm, H2O < 1.0 ppm; Innovative Technology) without exposure to air. 5/8-inch diameter disks were punched and weighed from the carbon paper to yield individual carbon cathodes. The weight of the active carbon layer (not including the carbon paper) averaged 1.0 mg ± 0.1 mg.

8.1.1.1.2 Electrolyte Preparation

LiNO3 and LiTFSI were heated under vacuum overnight at 100 °C to remove all traces of water and transferred directly into the glovebox. N,N-dimethylacetamide (DMA; Aldrich) and bis(2-methoxyethyl) ether (diglyme; Aldrich) solvents were dried over 3 Å molecular sieves (Aldrich). Lithium 2-bromoethanesulfonate was obtained through ion exchange with sodium 2-bromoethanesulfonate (Aldrich).

8.1.1.1.3 Coin Cell Assembly

First, a 1/2-inch (12.7 mm) diameter hole was punched in the top (cathode) side of each CR2032 case. Then, a stainless steel wire cloth disk, 3/4-inch (19 mm) disk diameter, and 0.0055-inch (0.140 mm) wire diameter from McMaster-Carr were added, followed by a cathode disk, ¾-inch diameter separator (either Whatman GF/D glass fiber or Celgard 3501), 100 μL of desired electrolyte, ½-inch diameter lithium metal, 15.5 mm diameter stainless steel spacer disk, stainless steel wave spring (MTI Corporation), and anode cap of the CR2032 case. The assembly was crimped to a pressure of 14 MPa with a hydraulic coin cell crimple (BT Innovations).

8.1.1.1.4 Testing Environment

Cells were tested at a regulated pure O2 environment of 1.3 atm and allowed to equilibrate for 6 h prior to electrochemical testing. Galvanostatic measurements were conducted using a Neware CT-3008 battery tester.

8.1.1.1.5 Cyclic Voltammetry

The cyclic voltammetry test was done in a two-electrode setup of Li||air cathode. The batteries were cycled between 1.9 V and 4.5 V at a scan rate of 1 mV/sec several times.

8.1.1.2 Anode Stability Methods and Materials

8.1.1.2.1 Impedance Spectroscopy

Cells in the symmetric configuration were assembled in an Ar glovebox. Measurements were done using a Solatron frequency analyzer at a frequency range of 10−3 to 107 Hz. The data was fitted into Nyquist-type plots using the equivalent circuit shown in Supplementary Fig. 10.2 with the software zsimpwin. Impedance was conducted at room temperature at various time intervals.

8.1.1.2.2 Linear Scan Voltammetry

Linear scan voltammetry was done in a Li||SS cell. The batteries were first swept to −0.2 V vs. Li/Li+; then they were swept in reverse direction until the voltage diverges.

8.1.1.2.3 Lithium Versus Stainless Steel Cycling

For cycling tests, lithium vs. stainless steel cells were prepared and were cycled at 0.01 mA/cm2 between 0 and 0.5 V ten times in order to form a stable SEI layer. Then different tests were done as given in the manuscript.

8.1.1.3 Characterization Techniques

8.1.1.3.1 Scanning Electron Microscopy and EDAX

Discharged cells were disassembled inside the glovebox, and the cathodes were removed and transported to the scanning electron microscope (Zeiss LEO 1550 Field Emission SEM) within an airtight container. The cathodes were loaded onto the stage in the presence of a nitrogen stream. Images were taken with a single pass after focusing on a nearby region. EDAX measurements were done by taking multiple counts on a small section of sample.

8.1.1.3.2 X-Ray Diffraction

Cathodes were mounted on a glass microscope slide inside an argon-filled glovebox and coated with paraffin oil to protect them from air during the X-ray diffraction (XRD) measurements. Measurements were done on a Scintag Theta-Theta X-ray diffractometer using Cu K-α radiation at λ = 1.5406 Å and fitted with a 2-dimensional detector. Frames were captured with an exposure time of 10 min, after which they were integrated along χ (the polar angle orthogonal to 2θ to yield an intensity) vs. 2θ plot.

8.1.1.3.3 X-Ray Photoelectron Spectroscopy

XPS was conducted surface science instruments SSX-100 with operating pressure of ~ 2 × 10−9 torr. Monochromatic Al K-α X-rays (1486.6 eV) with beam diameter of 1 mm were used. Photoelectrons were collected at an emission angle of 55°. A hemispherical analyzer determined electron kinetic energy, using a pass energy of 150 V for wide survey scans and 50 V for high-resolution scans. Samples were ion-etched using 4 kV Ar ions, which were rastered over an area of 2.25 × 4 mm with total ion beam current of 2 mA, to remove adventitious carbon. Spectra were referenced to adventitious C 1s at 284.5 eV. CasaXPS software was used for XPS data analysis with Shelby backgrounds. Li 1s and O 1s were assigned to single peaks for each bond, whereas Br 3d was assigned to double peaks (3d5/2 and 3d3/2) for each bond with 1.05 eV separation. Residual SD was maintained close to 1.0 for the calculated fits. Samples were exposed to air only during the short transfer time to the XPS chamber (less than 5 s).

Rights and permissions

Reprints and permissions

Copyright information

© 2019 Springer Nature Switzerland AG

About this chapter

Check for updates. Verify currency and authenticity via CrossMark

Cite this chapter

Choudhury, S. (2019). Designer Interphases for the Lithium-Oxygen Electrochemical Cell. In: Rational Design of Nanostructured Polymer Electrolytes and Solid–Liquid Interphases for Lithium Batteries. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-28943-0_8

Download citation

Publish with us

Policies and ethics

Search

Navigation