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Transcript
INVESTIGATING IONTRANSPORT AND THERMAL SAFETY IN FUNCTIONAL POLYMER SEPARATORS RISHI GUPTA, ROBERT K. EMMETT, MARGIE ARCILAVELEZ, JESSE KELLY MARK E. ROBERTS DR. ROBERTS’ RESEARCH GROUP DEPT. OF CHEMICAL ENGINEERING AND PHYSICS 1 Controlled Drug Delivery Motivation • Inefficient energy storage in lithium-ion batteries • Harmful effects of current battery materials on the environment • Carbon Materials • • Abundant in nature • Unknown/variable electrochemical properties using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells Thermal Runaway considerations This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Objectives using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Develop a smart material (electrolyte) that exhibits thermally responsive properties in nonaqueous systems •Ionic liquids (ILs) have negligible vapor pressure, are nonflammable, and thermally and chemically stable •Conductivity of systems remains constant or decreases above lower critical solution temperature (LCST) This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Ionic Liquids and Polymerization using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Dissolve poly(ethylene oxide) (PEO) in 1-ethyl-3-methylimidazolium tetrafluroborate ([C2mim][BF4]) via stirring in vacuum and nitrogen for 1 hour then heating for 17 hours at 80°C •Purification of benzyl methacrylate monomer using basic alumina •Polymerization of poly(benzyl methacrylate) (pBzMA) using 2,2’-azobis (2methylpropionitrile) at 65°C This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Experimental Methods using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Electrolyte solution placed in flat cell •Cell placed in oven to allow changes in temperature •Conductivity measured via electrochemical impedance spectroscopy (EIS) l RA This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Results and Discussion using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Phase separation occurs upon heating above LCST in PEO- [C2mim][BF4] and pBzMA- 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Results and Discussion using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Phase separation occurs upon heating above LCST in PEO- [C2mim][BF4] solutions This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Results and Discussion using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Conductivity of [C2mim][BF4] increases with increasing temperature •Conductivity of PEO- [C2mim][BF4] systems decreases above LCST Conductivity (mS/cm) Conductivity vs. Temperature 80 60 40 [C2mim][BF4] 20 80 wt% PEO [C2mim][BF4] 0 0 50 100 150 200 Conductivity vs. Temperature Temperature (Celsius) Conductivity (mS/cm) 4 3.5 3 2.5 2 80 wt% PEO [C2mim][BF4] 1.5 1 0.5 0 0 50 100 150 200 Temperature (Celsius) This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Results and Discussion using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Conductivity of [C2mim][BF4] increases with increasing temperature •Conductivity of PEO- [C2mim][BF4] systems decreases above LCST Conductivity vs. Temperature 16 Conductivity (mS/cm) 14 12 10 8 50 wt% PEO - [C2mim][BF4] 6 4 2 0 0 50 100 150 200 Temperature (Celsius) This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Results and Discussion using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Phase separation leads to higher resistance •Lower ion mobility in PEO phase Rmix RPEO RIL RT RPEO RIL This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Future Work using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Add lithium salts to PEO, [C2mim][BF4], and PEO- [C2mim][BF4] mixtures and again test conductivity with temperature This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Supercapacitors using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells • Supercapacitors causes current through charge separation • Porous membranes divide the electrodes • Prevents shorting • Carbon Nanotube Bucky Papers • Aromatic structure • nanocoils This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Electrolytes • Nonaqueous electrolytes • Wider voltage range • Propylene carbonate/acetonitrile • LiClO4, TBAF • Aqueous electrolytes • Strong acids • Smaller Ions have more mobility • Less peak separation • Tartic Acid does not corrode metals using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells 1M HClO4 1M Tartic Acid Kelly, J. C., et al. "Reversible Control of Electrochemical Properties using Thermally-Responsive Polymer Electrolytes." Advanced Materials 24.7 (2012): 886-9. Web This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Experimental Setup using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells • Electrochemical Treatment • Potential sweeps chemically alter the film • “activates” Fe remaining after synthesis • CV scans are run until steady state is reached • Analysis and characterization Standard battery analysis Determines how the film is altered This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Cyclic Voltammetry (CV) • Film changes properties • Scanned until a steady state using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells • Different Scan Rates • Shows electrochemical response w/ discharge time • Calculate capacitance This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Lignin Modification using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells • Second most abundant macromolecule • Used with acid electrolyte • Broadens redox peaks/ increases peak separation • Adsorption technique This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery using responsive membranes RIE with Lignin 120s Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells 90s 60s 30s NC 120s NC 30s 60s 90s • Argon etching increases surface area • Films soaked in lignin • No change without lignin This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Separator testing Scan 0.01 V/s using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells Charge/discharge data Separator Capacitance (F/g) CG 11.93 DW 12.42 CG Lig 8.6 DW Lig 9.98 • DW separators show slightly better performance • Lignin has unexpected result in this data This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Resistance of Separators • • • • using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells V/R=I, Variation of Ohm’s Law Larger current mean larger capacitances Nylon and Filter show best performance Consistent between lignin and non-lignin films 3mVs Nanocoil 10mVs Lignin Nanocoil This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Conclusions using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •Created a smart material that can lower conductivity with increasing temperature via LCST behavior •Electrolyte that safely shuts down batteries to prevent thermal runaway •Tartic acid does not corrode metals •Incorporating Lignin Increases Capacitance •RIE Increases surface area of the substrate •Nylon Membranes/Filter Paper membranes show best characteristics This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524. Controlled Drug Delivery Acknowledgements using responsive membranes Protein Separations for low cost therapeutics Energy Storage electrochemical devices and batteries Advanced Functional Membranes REU CO2 Recovery to reduce the impacts of climate change Water Purification Energy Conversion using self-cleaning membranes membranes in fuel cells •National Science Foundation •NASA •Dr. Arjun Rao This work was part of the National Science Foundation REU Site: Advanced Functional Membranes at Clemson University. Support was provided by NSF under award EEC 1061524.
