National Aeronautics and Space Administration! Recent Research in Lithium Batteries and Fuel ...
National Aeronautics and Space Administration!Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batter...
Lithium Polymer/Ionic Liquid Batteries Motivated by PERS program   Polymer Energy Rechargeable System. Advantages  S...
Our Objective Prepare polymer separator that has:  High lithium ion conductivity (~10-3 S/cm)  No volatile components...
National Aeronautics and Space Administration! GRC Polymer Electrolyte  Rod ...
Variables:A.  Amount of Room Temperature Ionic Liquid (RTIL) ~ 200, 300, 400%B.  Concentration of Lithium Bis(trifluorom...
Cycling Data Experiment 1: Amount of IL added200% IL with .5 mol/kg 300% IL with .5 mol/kg ...
Experiment 2: Concentration of LiTFSi 400% IL with .5 mol/kg 400% IL with .75 mol/kg T...
Experiment 3: Addition of Alumina400% IL with 1.0 mol/kg and 0% Alumina 400% IL with 1.0 mol/kg and 10% AluminaThe addit...
Impedance Data•  Addition of alumina results in a significant decrease in interfacial resistance •  More stable interf...
Summary  Made electrolytes by varying: 1.  Amount of RTIL 2.  Concentration of Li salt 3.  Addition of...
National Aeronautics and Space Administration! Progress of Proton Exchange Membrane (PEM) ...
National Aeronautics and Space Administration! www.nasa.gov 16
National Aeronautics and Space Administration! Advantanges •  Ef...
National Aeronautics and Space Administration! Proton Exchange Membrane must: •  ...
National Aeronautics and Space Administration! Nafion-State of the art membrane ...
National Aeronautics and Space Administration! Sulfonated Poly(arylene ether)s (McGrath) ...
National Aeronautics and Space Administration! Polybenzimidazole/H3PO4 (PBI) (CWRU) ...
National Aeronautics and Space Administration! Our Strategy: Synthesize Novel Polymer •  Fully Ar...
National Aeronautics and Space Administration! Solution: Poly(arylene ether triazine)s •  Full...
National Aeronautics and Space Administration! Monomer Synthesis ...
National Aeronautics and Space Administration! Polymer Synthesis • ...
National Aeronautics and Space Administration! Glass Transition Temperature ...
National Aeronautics and Space Administration! Polymer Sulfonation ...
National Aeronautics and Space Administration! 0.12 Co...
National Aeronautics and Space Administration! TEM Data DPA-PS...
National Aeronautics and Space Administration! Phosphoric Acid Uptake of DPA-PS/PBI Blends ...
National Aeronautics and Space Administration! Phosphoric acid uptake ...
National Aeronautics and Space Administration! Conclusions •  Sy...
Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries
Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries
Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries
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Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries

Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries presented by Allyson Palker and Dean Tigelaar of NASA's Glenn Research Center at an energy workshop on 7/20/2010.
Published on: Mar 4, 2016
Published in: Technology      Business      
Source: www.slideshare.net


Transcripts - Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries

  • 1. National Aeronautics and Space Administration! Recent Research in Lithium Batteries and Fuel Cells Dean Tigelaar Polymers Branch NASA Glenn Research Center www.nasa.gov 1
  • 2. National Aeronautics and Space Administration!Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries Allyson Palker, Dean Tigelaar Polymers Branch William Bennett Electrochemistry Branch NASA Glenn Research Center www.nasa.gov 2
  • 3. Lithium Polymer/Ionic Liquid Batteries Motivated by PERS program   Polymer Energy Rechargeable System. Advantages  Safety  Commercial batteries contain flammable solvents.  Li metal anodes Disadvantages  Lithium ion conductivity  Maximum conductivity ~10-4 S/cm *Gaston Narada International Ltd * 3
  • 4. Our Objective Prepare polymer separator that has:  High lithium ion conductivity (~10-3 S/cm)  No volatile components  High long term stability with lithium metal electrodes Strategy: Polymer gel electrolyte that contains ionic liquids  Nonvolatile, nonflammable, wide ESW. 4
  • 5. National Aeronautics and Space Administration! GRC Polymer Electrolyte  Rod segment provides mechanical strength.  PEO coil segment helps conduct lithium ions.  High degree of crosslinking.  Can hold large amounts of liquid additives (>400%). www.nasa.gov 5
  • 6. Variables:A.  Amount of Room Temperature Ionic Liquid (RTIL) ~ 200, 300, 400%B.  Concentration of Lithium Bis(trifluoromethane) sulfonimide (LiTFSi) ~ .5, .75, 1.0 mol/kgC.  Addition of Alumina (Al203) ~ 0, 5, 10, 15%
  • 7. Cycling Data Experiment 1: Amount of IL added200% IL with .5 mol/kg 300% IL with .5 mol/kg 400% IL is the most compatible with the Lithium electrodes at a current density of .25 mA/cm2, 60°C 10 400% IL with .5 mol/kg
  • 8. Experiment 2: Concentration of LiTFSi 400% IL with .5 mol/kg 400% IL with .75 mol/kg The concentration of Lithium salt that was the most compatible with the Lithium electrodes was the 1.0 mol/ kg. 11 400% IL with 1.0 mol/kg
  • 9. Experiment 3: Addition of Alumina400% IL with 1.0 mol/kg and 0% Alumina 400% IL with 1.0 mol/kg and 10% AluminaThe addition of 5% Alumina caused the Voltage to decrease five foldshowing there is less resistance and better stability in comparisonto the sample without Alumina. 12
  • 10. Impedance Data•  Addition of alumina results in a significant decrease in interfacial resistance •  More stable interfacial layer. 13
  • 11. Summary  Made electrolytes by varying: 1.  Amount of RTIL 2.  Concentration of Li salt 3.  Addition of Alumina  Symmetric coin cells made with the polymer electrolytes  Improved cycling stability in coin cells from <3 hrs to >1000 hrs at 0.25 mA/cm2 current density  400% IL with 1.0 mol/kg and 10% Alumina was the most compatible with the Lithium electrodes •  Tigelaar, D. M.; Palker, A. P.; Meador, M. A. B.; Bennett, W. R., J. Electrochem. Soc., 2008, 155, A768. 14
  • 12. National Aeronautics and Space Administration! Progress of Proton Exchange Membrane (PEM) Fuel Cells Dean Tigelaar, Allison Palker Polymers Branch NASA Glenn Research Center Huan He, Christine Jackson, Kellina Anderson, Tyler Peter, Jesse Wainright, Robert Savinell Case Western Reserve University www.nasa.gov 15
  • 13. National Aeronautics and Space Administration! www.nasa.gov 16
  • 14. National Aeronautics and Space Administration! Advantanges •  Efficient energy conversion (up to 70%) •  High energy density •  Generates water in exhaust •  No recharge needed Potential Uses •  Propulsion –  Automotive, zero emission aircraft •  Stationary –  Power supply (Gemini V) •  Portable –  Astronaut equipment •  Regenerative –  Coupled with photovoltaic systems for energy storage –  Hydrolysis of water back into H2 and O2 www.nasa.gov 17
  • 15. National Aeronautics and Space Administration! Proton Exchange Membrane must: •  Have high proton conductivity. •  Have low electrical conductivity. •  Be mechanically robust in the wet and dry state. •  Processable into thin film. •  Be stable to a high temperature, high humidity, highly acidic environment for thousands of hours. www.nasa.gov 18 18
  • 16. National Aeronautics and Space Administration! Nafion-State of the art membrane poly(perfluorosulfonic acid) “Nafion” Advantages: Disadvantages: • Excellent proton conductivity • Expensive (0.1 S/cm ) • Limited operation temperature • Good mechanical and chemical (≤80°C) properties •High methanol permeability. • Long-term stability www.nasa.gov 19
  • 17. National Aeronautics and Space Administration! Sulfonated Poly(arylene ether)s (McGrath) •  High thermal and chemical stability •  Good film forming properties •  Several monomers and polymers are commercially available •  Controlled degree of sulfonation –  Controls conductivity and mechanical properties –  30-40% sulfonated monomer www.nasa.gov 20
  • 18. National Aeronautics and Space Administration! Polybenzimidazole/H3PO4 (PBI) (CWRU) •  Excellent thermal and oxidative stability. •  Less dependant on humidification. •  Operating temperatures up to 200oC. •  High H3PO4 uptake (~200 wt%). •  But: Difficult to process into strong film. •  Produced commercially by BASF. www.nasa.gov 21
  • 19. National Aeronautics and Space Administration! Our Strategy: Synthesize Novel Polymer •  Fully Aromatic –  Thermo-oxidatively stable and mechanically strong. •  Heterocyclic –  Coordination with H3PO4 by acid-base or H-bonding. –  Similar to PBI but easier to process. •  Highly soluble in common organic solvents –  NMP, DMAc, CHCl3. www.nasa.gov 22
  • 20. National Aeronautics and Space Administration! Solution: Poly(arylene ether triazine)s •  Fully aromatic •  Soluble due to ether links and bulky pendant groups. •  Can be made conductive in 2 different ways. 1) Nitrogen groups capable of bonding with H3PO4 2) Can be sulfonated on exclusively on pendant groups www.nasa.gov 23
  • 21. National Aeronautics and Space Administration! Monomer Synthesis www.nasa.gov 24
  • 22. National Aeronautics and Space Administration! Polymer Synthesis •  High molecular weight (IV 0.6-1.0 dL/g). •  Thermo-oxidative stability (Td > 500°C in air). •  Rigid but soluble (Tg 150-290°C, soluble in CHCl3, NMP, CF3CO2H). •  Good film forming properties. www.nasa.gov 25
  • 23. National Aeronautics and Space Administration! Glass Transition Temperature www.nasa.gov 26
  • 24. National Aeronautics and Space Administration! Polymer Sulfonation www.nasa.gov 27
  • 25. National Aeronautics and Space Administration! 0.12 Conductivity of Sulfonated Films 0.1 0.08 Conductivity / S cm-1 0.06 0.04 0.02 Nafion 115 DPA-Pket DPA-diket DPA-PS 0 0 10 20 30 40 50 60 70 80 90 100 Temperature / oC • Most conductive film is more conductive than Nafion 117. • This film is brittle in it’s dry state, but can be fixed by changing to a more flexible monomer. •  The most conductive polymer was the lowest water uptake and ion exchange capacity. Why? Tigelaar, D. M.; Palker, A. P.; Jackson, C. M.; Anderson, K. M.; Wainright, J. Savinell, R. F Macromolecules, 2009, 42, 1888. www.nasa.gov 28
  • 26. National Aeronautics and Space Administration! TEM Data DPA-PS DPA-pket IEC = 1.88 meq/g IEC = 2.12 meq/g Water uptake = 131% Water uptake = 211% σ = 0.11 S/cm at 90°C σ = 0.082 S/cm at 90°C 2-10 nm hydrophilic regions 5-15 nm hydrophilic regions Dark background Well connected Tigelaar, D. M.; Palker, A. P.; He, R.; Scheiman D. A.; Petek, T.; Savinell, R. F.; Yoonessi, M. J. Membrane Science, 2011, 369, 455. www.nasa.gov 29
  • 27. National Aeronautics and Space Administration! Phosphoric Acid Uptake of DPA-PS/PBI Blends 900 800 700 600 Uptake (wt %) 500 Room Temp 50oC 90oC 400 1:1 DPA-PS:PBI 3:1 DPA-PS:PBI 300 9:1 DPA-PS:PBI 200 100 0 0 20 40 60 80 100 120 140 160 180 200 220 240 260 Time (hr) •  Uptake of PBI by this method is 200%. •  “As received” PBI can be used for 3:1, 9:1 blends. www.nasa.gov 30
  • 28. National Aeronautics and Space Administration! Phosphoric acid uptake 85% H3PO4 90°C 22 days100% 3:1 DPA-PS:PBI blend 7% polymer 93% H3PO4 www.nasa.gov 31
  • 29. National Aeronautics and Space Administration! Conclusions •  Synthesized novel poly(arylene ether)s that are fully aromatic, soluble, and with high molecular weight. •  Polymers have high H3PO4 uptake, but lose dimensional stability as high temperatures. •  Most conductive sulfonated polymer has the same conductivity as Nafion 115 at 100% RH. •  Most conductive polymer is brittle when dry. –  This problem can be fixed by replacing sulfone with isophthaloyl group or using a comonomer. Acknowledgements • Dan Scheiman, Mitra Yoonessi • Robert Savinell, Jesse Wainright, Christine Jackson, and Kellina Anderson, Huan He. www.nasa.gov 32

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