Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries

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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.

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  • OMK INDUSTRIES+WTCA: WE WANT TO INVEST AND BUILD ALKALINE BATTERY PLANT IN CHINA (We are interested in the following provinces for investment: Guangzhou area) and also need to find us Marketing company (for business plan) WE ARE GOING TO VISIT CHINA IN MARCH, AT THIS TIME, WE WANT TO VISIT GUANGZHOU AREA AND TO MEET AND TALK WITH LOCAL GOVERNMENT, MARKETING COMPANY AND WITH SUPPLIERS-FACTORIES OF EQUIPMENT FOR ALKALINE BATTERIES. MAYBE IN OCTOBER WE WILL FINISH THE TENDER AND DEFINE SUPPLIER OF COMPLETE PRODUCTION LINE. Our company World Trade Center Almaty" (WTCA) + "OMK Industries" going to invest for Alkaline Battery Factory in CHINA (We are interested of region: Guangzhou). Please urgently answer to the questions (for marketing analysis and equipment): 1} Where should the factory installed (What infrastructure there: proximity to road, rail, Where to buy raw materials for the plant?)? 2} What must be a sizes plant area (m2), for the following capacity of batteries?: Our capacity for the average manufacturing about ~ 120000 pcs/hour (200 pcs/min (ppm)) for each type batteries (Can You give advice to about of average productivity-capacity: pcs/hour)? 3} What should be the power of each equipment and common plant lines (Available Power)? 4} How much total price (cost) of complete line for Alkaline Batteries production: ~ 120000 pcs/hour (fully automatic line)? 5} What favorable conditions at region Guangzhou: raw materials, tax discounts, administrative support to the local authorities etc.? 6} Note: we do not have to use: Mercury and Cadmium free alkaline manganese battery, as required by of Chinese law! 7} Note: After this project, perhaps additional construction plant for recycling utilized alkaline batteries (separates the battery case metals, manganese and zinc)! 8} What is price (cost) of construction-building of Plant and cost of land (rent)) or maybe to buy or rent operating factory in the area Guangzhou for Alkaline Batteries Plant? 9} Where buy equipment (technological lines) for the production of Alkaline Batteries (China and other countries)? 10) Where buy additional Component equipment (technological lines): (Machines of metallurgical and metal cutting for Steel materials, Nickel plated steel cylindrical can (cell), Cap part; Machines of polymeric materials production (Nylon gasket, Cylindrical separator (fiberglass, PE, PP plastic film))? 11} Where to buy raw materials for the production of Alkaline Batteries: Steel, Nickel, Nylon, Fiberglass, PE, PP plastic film, Aluminum metalized PVC label, Zinc-Zn, Manganese dioxide-MnO2, Potassium hydroxide (caustic potash)-KOH, Zinc oxide, Iron oxide, Gelling agents, Graphite and other ingredients? 12} Advise for us distributorship and trading companies that can implement-realize (sell) our products in Chinese market! Also send flowsheet equipment location and size of the building and of course the detailed steps of the process. Please, you have to send me your commercial offers for the various types of Alkaline Batteries technology, Commercial offer with prices, Scheme of the process and technical features of the equipment with size. Please you help us to find Marketing company for marketing research and compilation business-plan. Our alkaline battery products must include production the following types batteries and equipment for this (do not know the name): LR20, LR14, LR6, LR03, 6LR61 alkaline batteries. Below are photos for example:Best regards, Galymbek Baimakhanov, Technical manager. Company "World Trade Center Almaty" (WTCA) + "OMK Industries", 42 Timiryazev str., Almaty, Kazakhstan, Tel /fax: +7 (727) 2742424, Mob tel.: +7 7772040185(WhatsApp-WeChat-Viber), +7 7017532115, E-mail: otcheg@mail.ru, Skype: Galymbekb,
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Polymer/Ionic Liquid Electrolytes and Their Potential in Lithium Batteries

  1. 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. 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. 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. 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. 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. 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. 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. 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. 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. 10. Impedance Data•  Addition of alumina results in a significant decrease in interfacial resistance •  More stable interfacial layer. 13
  11. 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. 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. 13. National Aeronautics and Space Administration! www.nasa.gov 16
  14. 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. 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. 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. 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. 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. 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. 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. 21. National Aeronautics and Space Administration! Monomer Synthesis www.nasa.gov 24
  22. 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. 23. National Aeronautics and Space Administration! Glass Transition Temperature www.nasa.gov 26
  24. 24. National Aeronautics and Space Administration! Polymer Sulfonation www.nasa.gov 27
  25. 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. 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. 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. 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. 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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