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Sample records for solid-state polymer electrolytes

  1. Lithium Polymer Electrolytes and Solid State NMR

    NASA Technical Reports Server (NTRS)

    Berkeley, Emily R.

    2004-01-01

    Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for

  2. Lithium Polymer Electrolytes and Solid State NMR

    NASA Technical Reports Server (NTRS)

    Berkeley, Emily R.

    2004-01-01

    Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for

  3. All-solid-state proton battery using gel polymer electrolyte

    SciTech Connect

    Mishra, Kuldeep; Pundir, S. S.; Rai, D. K.

    2014-04-24

    A proton conducting gel polymer electrolyte system; PMMA+NH{sub 4}SCN+EC/PC, has been prepared. The highest ionic conductivity obtained from the system is 2.5 × 10−4 S cm{sup −1}. The optimized composition of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO{sub 4}⋅7H{sub 2}O anode and MnO{sub 2} cathode. The open circuit voltage of the battery is 1.4 V and the highest energy density is 5.7 W h kg−1 for low current drain.

  4. Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

    NASA Astrophysics Data System (ADS)

    Pandey, G. P.; Hashmi, S. A.

    2013-12-01

    Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ˜2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ˜127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ˜76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

  5. TOPICAL REVIEW: Solid polymer electrolytes: materials designing and all-solid-state battery applications: an overview

    NASA Astrophysics Data System (ADS)

    Agrawal, R. C.; Pandey, G. P.

    2008-11-01

    Polymer electrolytes are promising materials for electrochemical device applications, namely, high energy density rechargeable batteries, fuel cells, supercapacitors, electrochromic displays, etc. The area of polymer electrolytes has gone through various developmental stages, i.e. from dry solid polymer electrolyte (SPE) systems to plasticized, gels, rubbery to micro/nano-composite polymer electrolytes. The polymer gel electrolytes, incorporating organic solvents, exhibit room temperature conductivity as high as ~10-3 S cm-1, while dry SPEs still suffer from poor ionic conductivity lower than 10-5 S cm-1. Several approaches have been adopted to enhance the room temperature conductivity in the vicinity of 10-4 S cm-1 as well as to improve the mechanical stability and interfacial activity of SPEs. In this review, the criteria of an ideal polymer electrolyte for electrochemical device applications have been discussed in brief along with presenting an overall glimpse of the progress made in polymer electrolyte materials designing, their broad classification and the recent advancements made in this branch of materials science. The characteristic advantages of employing polymer electrolyte membranes in all-solid-state battery applications have also been discussed.

  6. 'All-solid-state' electrochemistry of a protein-confined polymer electrolyte film

    SciTech Connect

    Parthasarathy, Meera; Pillai, Vijayamohanan K. Mulla, Imtiaz S.; Shabab, Mohammed; Khan, M.I.

    2007-12-07

    Interfacial redox behavior of a heme protein (hemoglobin) confined in a solid polymer electrolyte membrane, Nafion (a perfluoro sulfonic acid ionomer) is investigated using a unique 'all-solid-state' electrochemical methodology. The supple phase-separated structure of the polymer electrolyte membrane, with hydrophilic pools containing solvated protons and water molecules, is found to preserve the incorporated protein in its active form even in the solid-state, using UV-visible, Fluorescence (of Tryptophan and Tyrosine residues) and DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy. More specifically, solid-state cyclic voltammetry and electrochemical impedance of the protein-incorporated polymer films reveal that the Fe{sup 2+}-form of the entrapped protein is found to bind molecular oxygen more strongly than the native protein. In the 'all-solid-state' methodology, as there is no need to dip the protein-modified electrode in a liquid electrolyte (like the conventional electrochemical methods), it offers an easier means to study a number of proteins in a variety of polymer matrices (even biomimetic assemblies). In addition, the results of the present investigation could find interesting application in a variety of research disciplines, in addition to its fundamental scientific interest, including protein biotechnology, pharmaceutical and biomimetic chemistry.

  7. 'All-solid-state' electrochemistry of a protein-confined polymer electrolyte film.

    PubMed

    Parthasarathy, Meera; Pillai, Vijayamohanan K; Mulla, Imtiaz S; Shabab, Mohammed; Khan, M I

    2007-12-07

    Interfacial redox behavior of a heme protein (hemoglobin) confined in a solid polymer electrolyte membrane, Nafion (a perfluoro sulfonic acid ionomer) is investigated using a unique 'all-solid-state' electrochemical methodology. The supple phase-separated structure of the polymer electrolyte membrane, with hydrophilic pools containing solvated protons and water molecules, is found to preserve the incorporated protein in its active form even in the solid-state, using UV-visible, Fluorescence (of Tryptophan and Tyrosine residues) and DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy. More specifically, solid-state cyclic voltammetry and electrochemical impedance of the protein-incorporated polymer films reveal that the Fe2+-form of the entrapped protein is found to bind molecular oxygen more strongly than the native protein. In the 'all-solid-state' methodology, as there is no need to dip the protein-modified electrode in a liquid electrolyte (like the conventional electrochemical methods), it offers an easier means to study a number of proteins in a variety of polymer matrices (even biomimetic assemblies). In addition, the results of the present investigation could find interesting application in a variety of research disciplines, in addition to its fundamental scientific interest, including protein biotechnology, pharmaceutical and biomimetic chemistry.

  8. All solid-state electric double-layer capacitors based on alkaline polyvinyl alcohol polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Yang, Chun-Chen; Hsu, Sung-Ting; Chien, Wen-Chen

    Solid-state electrochemical double-layer capacitors (ELDCs) based on alkaline polyvinyl alcohol (PVA) solid polymer electrolytes (SPEs) are prepared. Electrochemical capacitance performance of these capacitors is studied by cyclic voltammetry, galvanostatic charge-discharge testing, and ac impedance spectroscopy. For comparison, two types of EDLC cells are constructed and tested. It is found that an EDLC with a PVA polymer electrolyte exhibits much higher capacitance and longer cycle-life than one with the PP/PE separator. The specific capacitance for the EDLC with the PVA-based SPE is in the range of 100-112 F g -1, and depends on the scan rate or the charge-discharge current rates. The results also indicate that the solid-state EDLC shows a relatively stable specific capacitance of 100 F g -1 after 1000 cycles. The findings suggest that the PVA-based SPE is a promising material for use in EDLCs.

  9. Potential of polymethacrylate pseudo crown ethers as solid state polymer electrolytes.

    PubMed

    Moins, S; Martins, J C; Krumpmann, A; Lemaur, V; Cornil, J; Delbosc, N; Decroly, A; Dubois, Ph; Lazzaroni, R; Gohy, J-F; Coulembier, O

    2017-06-22

    The association of kinetic studies, DFT calculations and (1)H-(7)Li NMR analyses allowed the control of the cyclo-ATRP of PEG9DMA and the production of polymethacrylate pseudo crown-ethers of various molar masses. Their potential to act as a solid-state polymer electrolyte in Li-ion batteries has been highlighted and may come from the supramolecular organization of the cyclo-PEG forming a Li(+) diffusion channel.

  10. Polymer-Rich Composite Electrolytes for All-Solid-State Li-S Cells.

    PubMed

    Judez, Xabier; Zhang, Heng; Li, Chunmei; Eshetu, Gebrekidan Gebresilassie; Zhang, Yan; González-Marcos, José A; Armand, Michel; Rodriguez-Martinez, Lide M

    2017-08-03

    Polymer-rich composite electrolytes with lithium bis(fluorosulfonyl)imide/poly(ethylene oxide) (LiFSI/PEO) containing either Li-ion conducting glass ceramic (LICGC) or inorganic Al2O3 fillers are investigated in all-solid-state Li-S cells. In the presence of the fillers, the ionic conductivity of the composite polymer electrolytes (CPEs) does not increase compared to the plain LiFSI/PEO electrolyte at various tested temperatures. The CPE with Al2O3 fillers improves the stability of the Li/electrolyte interface, while the Li-S cell with a LICGC-based CPE delivers high sulfur utilization of 1111 mAh g(-1) and areal capacity of 1.14 mAh cm(-2). In particular, the cell performance gets further enhanced when combining these two CPEs (Li | Al2O3-CPE/LICGC-CPE | S), reaching a capacity of 518 mAh g(-1) and 0.53 mAh cm(-2) with Coulombic efficiency higher than 99% at the end of 50 cycles at 70 °C. This study shows that the CPEs can be promising electrolyte candidates to develop safe and high-performance all-solid-state Li-S batteries.

  11. All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode.

    PubMed

    Zhu, Zhiqiang; Hong, Meiling; Guo, Dongsheng; Shi, Jifu; Tao, Zhanliang; Chen, Jun

    2014-11-26

    The cathode capacity of common lithium ion batteries (LIBs) using inorganic electrodes and liquid electrolytes must be further improved. Alternatively, all-solid-state lithium batteries comprising the electrode of organic compounds can offer much higher capacity. Herein, we successfully fabricated an all-solid-state lithium battery based on organic pillar[5]quinone (C35H20O10) cathode and composite polymer electrolyte (CPE). The poly(methacrylate) (PMA)/poly(ethylene glycol) (PEG)-LiClO4-3 wt % SiO2 CPE has an optimum ionic conductivity of 0.26 mS cm(-1) at room temperature. Furthermore, pillar[5]quinine cathode in all-solid-state battery rendered an average operation voltage of ∼2.6 V and a high initial capacity of 418 mAh g(-1) with a stable cyclability (94.7% capacity retention after 50 cycles at 0.2C rate) through the reversible redox reactions of enolate/quinonid carbonyl groups, showing favorable prospect for the device application with high capacity.

  12. All solid-state comb-like network polymer electrolytes based on poly(methylsiloxane)

    NASA Astrophysics Data System (ADS)

    Jiang, Hui; Fang, Shibi

    All solid-state comb-like network polymer electrolytes (CNPE) based on poly(methylsiloxane) with pendant PEO chains as internal plasticizing chains (IPC) have been designed and synthesized. Ultraviolet (UV) polymerization method was applied for the curing of CNPEs. Effects of the network structure on the conductive properties and mechanical properties were discussed in details. Ionic conductivity of the prepared CNPE is one order of magnitude larger than those without IPCs, which suggests that the expected drop of conductivity caused by crosslinking has been well compensated by the introduction of IPCs. Maximum conductivity of 1.01 × 10 -4 S cm -1 and maximum tensile strength of 0.66 MPa were obtained at 30 °C. Electrochemical stability and electrolyte/electrodes interfacial stability properties were evaluated by cyclic voltammetry and ac impedance, respectively.

  13. Solid-state sodium batteries using polymer electrolytes and sodium intercalation electrode materials

    SciTech Connect

    Ma, Y. |

    1996-08-01

    Solid-state sodium cells using polymer electrolytes (polyethylene oxide mixed with sodium trifluoromethanesulfonate: PEO{sub n}NaCF{sub 3}SO{sub 3}) and sodium cobalt oxide positive electrodes are characterized in terms of discharge and charge characteristics, rate capability, cycle life, and energy and power densities. The P2 phase Na{sub x}CoO{sub 2} can reversibly intercalate sodium in the range of x = 0.3 to 0.9, giving a theoretical specific energy of 440 Wh/kg and energy density of 1,600 Wh/l. Over one hundred cycles to 60% depth of discharge have been obtained at 0.5 mA/cm{sup 2}. Experiments show that the electrolyte/Na interface is stable and is not the limiting factor to cell cycle life. Na{sub 0.7}CoO{sub 2} composite electrodes containing various amounts of carbon black additive are investigated. The transport properties of polymer electrolytes are the critical factors for performance. These properties (the ionic conductivity, salt diffusion coefficient, and ion transference number) are measured for the PEO{sub n}NaCF{sub 3}SO{sub 3} system over a wide range of concentrations at 85 C. All the three transport properties are very salt-concentration dependent. The ionic conductivity exhibits a maximum at about n = 20. The transference number, diffusion coefficient, and thermodynamic factor all vary with salt concentration in a similar fashion, decreasing as the concentration increases, except for a local maximum. These results verify that polymer electrolytes cannot be treated as ideal solutions. The measured transport-property values are used to analyze and optimize the electrolytes by computer simulation and also cell testing. Salt precipitation is believed to be the rate limiting process for cells using highly concentrated solutions, as a result of lower values of these properties, while salt depletion is the limiting factor when a dilute solution is used.

  14. All Solid-State Lithium Metal Batteries Using Cross-linked Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Pan, Qiwei; Li, Christopher; Soft Materials Team

    Nowadays, to prepare all solid-state lithium metal batteries with high rate capability and stability using solid polymer electrolytes (SPEs) is still a grand challenge because of the interfaces between the SPE and the electrodes. In this presentation, we report a series of hybrid SPEs with controlled network structures by using POSS as cross-linker. These hybrid network SPEs show promising ionic conductivity, mechanical properties, and lithium dendrite growth resistance. All solid-state LiFePO4/Li batteries were also prepared using these SPEs as the electrolytes to study the effect of conductivity and mechanical properties of the SPEs on the performance of the batteries. At 90 °C, the prepared cells show high rate capability and stability. Capacity up to 160 mAh/g can be obtained at a C/2 rate during the galvanostatic cycling. Capacity retention of the cells is higher than 80% after 250 cycles. Battery performance at 60 °C and decay mechanism of the batteries will also be discussed.

  15. Thin and flexible solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes for device applications.

    PubMed

    Howlett, Patrick C; Ponzio, Florian; Fang, Jian; Lin, Tong; Jin, Liyu; Iranipour, Nahid; Efthimiadis, Jim

    2013-09-07

    All solid-state organic ionic plastic crystal-polymer nanofibre composite electrolytes are described for the first time. The new composite materials exhibit enhanced conductivity, excellent thermal, mechanical and electrochemical stability and allow the production of optically transparent, free-standing, flexible, thin film electrolytes (10's μms thick) for application in electrochemical devices. Stable cycling of a lithium cell incorporating the new composite electrolyte is demonstrated, including cycling at lower temperatures than previously possible with the pure material.

  16. A new solid-state electrolyte: Rubbery 'polymer-in-salt' containing LiN(CF 3SO 2) 2

    NASA Astrophysics Data System (ADS)

    Feng, Li; Cui, Hailin

    A new class of rubbery 'polymer-in-salt' electrolytes for application in solid-state lithium batteries has been explored by differential scanning calorimetry and a.c. impedance analysis. Simple phase diagrams of LiN(CF 3SO 2) 2+LiClO 4 and LiC(CF 3SO 2) 3+LiN(CF 3SO 2) 2 have been drawn, which are very important to determine polymer-in-salt electrolyte materials. The conductivities obtained by a.c. impedance measurement are smaller for the electrolyte that contains acetate LiOAc salt than for the electrolyte without this salt.

  17. Optimized performance of quasi-solid-state DSSC with PEO-bismaleimide polymer blend electrolytes filled with a novel procedure.

    PubMed

    Lee, Dong Ha; Sun, Kyung Chul; Qadir, Muhammad Bilal; Jeong, Sung Hoon

    2014-12-01

    Dye-sensitized solar cell (DSSC) is an attractive renewable energy technology currently under intense investigation. Electrolyte plays an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. In this study, DSSC is developed by using quasi-solid electrolyte and a novel procedure is adopted for filling this electrolyte. The quasi-solid-state electrolyte was prepared by mixing Poly ethylene oxide (PEO) and bismaleimide together and constitution was taken as PEO (15 wt%) at various bismaleimide concentrations (1, 3, 5 wt%). The novel procedure of filling electrolyte consists of three major steps (first step: filling liquid electrolyte, second step: vaporization of liquid electrolyte, third step: refilling quasi-solid-state electrolyte). The electrochemical and photovoltaic performances of DSSCs with these electrolytes were also investigated. The electrochemical impedance spectroscopy (EIS) indicated that TiO2/Dye/electrolyte impedance is reduced and electron lifetime is increased, and consequently efficiency of cell has been improved after using this novel procedure. The photovoltaic power conversion efficiency of 6.39% has been achieved under AM 1.5 simulated sunlight (100 W/cm2) through this novel procedure and by using specified blend of polymers.

  18. Superionic solid-state polymer electrolyte membrane for high temperature applications

    NASA Astrophysics Data System (ADS)

    Kyu, Thein; He, Ruixuan; Cao, Jinwei

    2015-03-01

    Completely amorphous, flexible, solid-state polymer electrolyte membranes (ss-PEM) consisted of polyethylene glycol diacrylate /succinonitrile plasticizer (SCN)/lithium trifluorosulfonyl imide were fabricated via UV polymerization. The room temperature ionic conductivity of our ss-PEM is extremely high (i.e., 10-3S/cm), which is already in the superionic conductor range of inorganic and/or liquid electrolyte counterparts. Of particular interest is that our ss-PEM is thermally stable up to 140°C, which is superior to the liquid electrolyte counterpart that degrades above 80°C. The ss-PEM exhibits cyclic stability in both LiFePO4/Li and Li4Ti5O12 /Li half-cells up to 50 cycles tested. The trend of conductivity enhancement with temperature is reproducible in the repeated cycles, showing melting transitions of the SCN plastic crystals. In the compositions close to the solid (SCN plastic crystal)-liquid coexistence line, polymerization-induced crystallization occurs during photo-curing. The effect of solid-liquid segregation on ionic conductivity behavior is discussed. Supported by NSF-DMR 1161070.

  19. Superior Blends Solid Polymer Electrolyte with Integrated Hierarchical Architectures for All-Solid-State Lithium Ion Batteries.

    PubMed

    Zhang, Dechao; Zhang, Long; Yang, Kun; Wang, Hongqiang; Yu, Chuang; Xu, Di; Xu, Bo; Wang, Li-Min

    2017-10-06

    Exploration of advanced solid electrolytes with good interfacial stability toward electrodes is a highly relevant research topic for all-solid-state batteries. Here, we report PCL/SN blends integrating with PAN-skeleton as solid polymer electrolyte prepared by a facile method. This polymer electrolyte with hierarchical architectures exhibits high ionic conductivity, large electrochemical windows, high degree flexibility, good flame-retardance ability, and thermal stability (workable at 80 °C). Additionally, it demonstrates superior compatibility and electrochemical stability toward metallic Li as well as LiFePO4 cathode. The electrolyte/electrode interfaces are very stable even subjected to 4.5 V at charging state for long time. The LiFePO4/Li all-solid-state cells based on this electrolyte deliver high capacity, outstanding cycling stability, and superior rate capability better than those based on liquid electrolyte. This solid polymer electrolyte is eligible for next generation high energy density all-solid-state batteries.

  20. Structure and ionic interactions of organic-inorganic composite polymer electrolytes studied by solid-state NMR and Raman spectroscopy.

    PubMed

    Joo, Chan Gyu; Bronstein, Lyudmila M; Karlinsey, Robert L; Zwanziger, Josef W

    2002-01-01

    Solid-state NMR studies of composite polymer electrolytes are reported. The materials consist of polyethylene oxide and an organic inorganic composite, together with a lithium salt, and are candidates for electrolytes in solid-state lithium ion batteries. Silicon and aluminum MAS and multiple quantum MAS are used to characterize the network character of the organic-inorganic composite, and spin diffusion measurements are used to determine the nanostructure of the polymer/composite blending. Multiple quantum spin counting is used to measure the ion aggregation. The NMR results are supported by Raman spectra, calorimetry, and impedance spectroscopy. From these experiments it is concluded that the composite suppresses polymer crystallization without suppressing its local mobility, and also suppresses the tendency for the ions to aggregate. This polymer composite thus appears very promising for application in lithium ion batteries.

  1. Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

    NASA Astrophysics Data System (ADS)

    Tiruye, Girum Ayalneh; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2016-09-01

    Four Ionic Liquid based Polymer Electrolytes (IL-b-PE) were prepared by blending a Polymeric Ionic Liquid, Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PILTFSI), with four different ionic liquids: 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (IL-b-PE1), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (IL-b-PE2), 1-(2-hydroxy ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HEMimTFSI) (IL-b-PE3), and 1-Butyl-1-methylpyrrolidinium dicyanamide, (PYR14DCA) (IL-b-PE4). Physicochemical properties of IL-b-PE such as ionic conductivity, thermal and electrochemical stability were found to be dependent on the IL properties. For instance, ionic conductivity was significantly higher for IL-b-PE2 and IL-b-PE4 containing IL with small size anions (FSI and DCA) than IL-b-PE1 and IL-b-PE3 bearing IL with bigger anion (TFSI). On the other hand, wider electrochemical stability window (ESW) was found for IL-b-PE1 and IL-b-PE2 having ILs with electrochemically stable pyrrolidinium cation and FSI and TFSI anions. Solid state Supercapacitors (SCs) were assembled with activated carbon electrodes and their electrochemical performance was correlated with the polymer electrolyte properties. Best performance was obtained with SC having IL-b-PE2 that exhibited a good compromise between ionic conductivity and electrochemical window. Specific capacitance (Cam), real energy (Ereal) & real power densities (Preal) as high as 150 F g-1, 36 Wh kg-1 & 1170 W kg-1 were found at operating voltage of 3.5 V.

  2. All-Solid-State Lithium-Ion Batteries with Grafted Ceramic Nanoparticles Dispersed in Solid Polymer Electrolytes.

    PubMed

    Lago, Nerea; Garcia-Calvo, Oihane; Lopez del Amo, Juan Miguel; Rojo, Teofilo; Armand, Michel

    2015-09-21

    Lithium-based rechargeable batteries offer superior specific energy and power, and have enabled exponential growth in industries focused on small electronic devices. However, further increases in energy density, for example for electric transportation, face the challenge of harnessing the lithium metal as negative electrode instead of limited-capacity graphite and its heavy copper current collector. All-solid-state batteries utilize solid polymer electrolytes (SPEs) to overcome the safety issues of liquid electrolytes. We demonstrate an all-solid-state lithium-ion battery by using plasticized poly(ethylene oxide)-based SPEs comprising anions grafted or co-grafted onto ceramic nanoparticles. This new approach using grafted ceramic nanoparticles enables the development of a new generation of nanohybrid polymer electrolytes with high ionic conductivity as well as high electrochemical and mechanical stability, enabling Li-ion batteries with long cycle life.

  3. Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

    2016-10-01

    A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

  4. Non-aqueous gel polymer electrolyte with phosphoric acid ester and its application for quasi solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Łatoszyńska, Anna A.; Żukowska, Grażyna Zofia; Rutkowska, Iwona A.; Taberna, Pierre-Louis; Simon, Patrice; Kulesza, Pawel J.; Wieczorek, Władysław

    2015-01-01

    A mechanically-stable non-aqueous proton-conducting gel polymer electrolyte that is based on methacrylate monomers, is considered here for application in solid-state type supercapacitors. An electrochemical cell using activated carbon as active materials and the new gel polymer electrolyte has been characterized at room temperature using cyclic voltammetry, galvanostatic charge-discharge cycle tests as well as impedance spectroscopy. The use of phosphoric acid ester (instead of phosphoric acid) as a proton donor has led to an increase of both the operation voltage window (up to 1.3 V) and the electrolyte ionic conductivity (on the level of an order of magnitude). The resulting double layer capacitance of the microporous activated carbon was found to be as high as 120 F g-1; even more important, the supercapacitor utilizing non-aqueous proton-conducting gel polymer electrolyte is well-behaved in the wide temperature range (namely, from -40 to 80 °C).

  5. Solid state electrolyte systems

    SciTech Connect

    Pederson, L.R.; Armstrong, B.L.; Armstrong, T.R.

    1997-12-01

    Lanthanum gallates are a new family of solid electrolytes that exhibit high ionic conductivity and are stable to high temperatures. Compositions have been developed that are as much as a factor of two more conductive than yttria-stabilized zirconia at a given temperature, through partial replacement of lanthanum by calcium, strontium, and/or barium and through partial replacement of gallium by magnesium. Oxide powders were prepared using combustion synthesis techniques developed in this laboratory; these were sintered to >95% of theoretical density and consisted of a single crystalline phase. Electrical conductivities, electron and ion transference numbers, thermal expansion, and phase behavior were evaluated as a function of temperature and oxygen partial pressure. A key advantage of the use of lanthanum gallate electrolytes in solid oxide fuel cells is that the temperature of operation may be lowered to perhaps 800 C, yet provide approximately the same power density as zirconia-based cells operating at 1000 C. Ceramic electrolytes that conduct both oxygen ions and electrons are potentially useful to passively separate pure oxygen from an air source at low cost. In such materials, an oxygen ion flux in one direction is charge-compensated by an opposing electron flux. The authors have examined a wide range of mixed ion and electron conducting perovskite ceramics in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, where M = Sr, Ca, and Ba, and N = Pr, Mn, Ni, Cu, Ti, and Al, as well as mixed conducting brownmillerite ceramics, and have characterized oxygen permeation behavior, defect chemistry, structural and phase stability, and performance as cathodes.

  6. Ion Dynamics in Solid-State Polymer Electrolyte Electrochemical Cells using in situ Time-Resolved Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Richey, Francis; Elabd, Yossef

    2012-02-01

    Understanding ion transport in solid-state polymer electrochemical cells is of great interest for the advancement of cell efficacy. However, currently there is limited experimental knowledge of ion transport on a molecular level. In this study, we report a new spectroelectrochemical experimental technique that provides in situ molecular level detail about cation and anion transport of an ionic liquid in solid-state polymer electrolyte electrochemical cells. In situ time-resolved Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy was utilized to measure the time dependent accumulation of ions at the cathode and anode interface under an applied potential. The results show that the cation and anion of the ionic liquid both transport and accumulate at the cathode under dry conditions, but only the cation accumulates at the cathode under humid conditions. This experiment was coupled with electrochemical impedance spectroscopy to simultaneously measure overall charge transport and cyclic voltammograms.

  7. Lithium Bis(fluorosulfonyl)imide/Poly(ethylene oxide) Polymer Electrolyte for All Solid-State Li-S Cell.

    PubMed

    Judez, Xabier; Zhang, Heng; Li, Chunmei; González-Marcos, José Antonio; Zhou, Zhi-Bin; Armand, Michel; Rodriguez-Martinez, Lide Mercedes

    2017-04-13

    Solid polymer electrolytes (SPEs) comprising lithium bis(fluorosulfonyl)imide (Li[N(SO2F)2], LiFSI) and poly(ethylene oxide) (PEO) have been studied as electrolyte material and binder for the Li-S polymer cell. The LiFSI-based Li-S all solid polymer cell can deliver high specific discharge capacity of 800 mAh gsulfur-1 (i.e., 320 mAh gcathode-1), high areal capacity of 0.5 mAh cm-2 and relatively good rate capability. The cycling performances of Li-S polymer cell with LiFSI are significantly improved compared to with those with conventional LiTFSI (Li[N(SO2CF3)2]) salt in the polymer membrane, due to the improved stability of the Li anode/electrolyte interphases formed in the LiFSI-based SPEs. These results suggest that the LiFSI-based SPEs are attractive electrolyte materials for solid-state Li-S batteries.

  8. All-solid state supercapacitors operating at 3.5 V by using ionic liquid based polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Ayalneh Tiruye, Girum; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2015-04-01

    All-solid state supercapacitors (SCs) using Ionic Liquid based Polymer Electrolyte (IL-b-PE) and activated carbon were assembled and characterized electrochemically. IL-b-PE consisted of a binary blend of a polymeric ionic liquid (PIL), poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (pDADMATFSI), and their corresponding ionic liquid (IL), N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR14TFSI) in a ratio of 40:60,w/w respectively. Assembling of supercapacitors simply consists of facing two impregnated electrodes without the need of additional separator. Several all-solid state SCs with impregnation ratios (IL-b-PE mass/active material mass) ranging from 5 to 18 were characterized. An all-solid state SC with impregnation ratio of 7 showed the best performance with specific capacitance (Cam) and real energy (Ereal) of 100 F g-1 and 32 Wh kg-1, respectively. After increasing temperatures to 60 °C, the performance of SCs further improved exhibiting Ereal values of 42 Wh kg-1 at 1 mA cm-2. These figures of merit are only slightly lower than those obtained for convectional SCs using pure PYR14TFS and much higher as compared with other solid SCs based on conventional polymer electrolytes. This is mainly due to the high electrochemical stability of this IL-b-PE that allows these solid SCs to operate at maximum voltages as high as 3.5 V for the first time.

  9. High-Performance Flexible Solid-State Supercapacitor with an Extended Nanoregime Interface through in Situ Polymer Electrolyte Generation.

    PubMed

    Anothumakkool, Bihag; Torris A T, Arun; Veeliyath, Sajna; Vijayakumar, Vidyanand; Badiger, Manohar V; Kurungot, Sreekumar

    2016-01-20

    Here, we report an efficient strategy by which a significantly enhanced electrode-electrolyte interface in an electrode for supercapacitor application could be accomplished by allowing in situ polymer gel electrolyte generation inside the nanopores of the electrodes. This unique and highly efficient strategy could be conceived by judiciously maintaining ultraviolet-triggered polymerization of a monomer mixture in the presence of a high-surface-area porous carbon. The method is very simple and scalable, and a prototype, flexible solid-state supercapacitor could even be demonstrated in an encapsulation-free condition by using the commercial-grade electrodes (thickness = 150 μm, area = 12 cm(2), and mass loading = 7.3 mg/cm(2)). This prototype device shows a capacitance of 130 F/g at a substantially reduced internal resistance of 0.5 Ω and a high capacitance retention of 84% after 32000 cycles. The present system is found to be clearly outperforming a similar system derived by using the conventional polymer electrolyte (PVA-H3PO4 as the electrolyte), which could display a capacitance of only 95 F/g, and this value falls to nearly 50% in just 5000 cycles. The superior performance in the present case is credited primarily to the excellent interface formation of the in situ generated polymer electrolyte inside the nanopores of the electrode. Further, the interpenetrated nature of the polymer also helps the device to show a low electron spin resonance and power rate and, most importantly, excellent shelf-life in the unsealed flexible conditions. Because the nature of the electrode-electrolyte interface is the major performance-determining factor in the case of many electrochemical energy storage/conversion systems, along with the supercapacitors, the developed process can also find applications in preparing electrodes for the devices such as lithium-ion batteries, metal-air batteries, polymer electrolyte membrane fuel cells, etc.

  10. Nano-Sponge Ionic Liquid-Polymer Composite Electrolytes for Solid-State Lithium Power Sources

    DTIC Science & Technology

    2010-01-01

    images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these... thin film batteries, 150 charge–discharge cycles are run for LixCoO2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects...9702;C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate

  11. Effect of random p-n junctions on quasi-solid-state dye-sensitized solar cells with polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Cui, Jiarui; Yang, Ying; Yi, Pengfei; Guo, Xueyi

    2014-12-01

    In this paper, the effect of p-n junction additives via blending p-type semiconductors (NiO and CuI) with n-type TiO2 in polymer electrolyte on quasi-solid-state DSSCs is studied. The conduction mechanism of DSSCs modified with random p-n junctions has been investigated by FTIR, SEM, UV-Vis and electrochemical analysis. The results indicate that the CuI-TiO2 p-n blend modified polymer electrolyte reaches the maximum ionic conductivity of 6.44 mS cm-1, which is almost twice over than that of pure-TiO2 modified one. From photovoltaic study, it is found that introducing CuI-TiO2 and NiO-TiO2 p-n blends in polymer electrolyte can obviously improve electron recombination and light-to-electric conversion efficiency of DSSCs. The conversion efficiency of CuI-TiO2 p-n blend modified DSSC is 3.34%, which is much higher than that of pure TiO2 modified device (1.76%). It is also demonstrated that the photovoltaic properties of DSSCs directly depends on the ratio of p-type CuI and n-type TiO2 in the p-n blends and the optimal conversion efficiency of 4.27% is obtained at CuI:TiO2 ratio of 4:1.

  12. Safety of solid-state Li metal battery: Solid polymer versus liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Perea, Alexis; Dontigny, Martin; Zaghib, Karim

    2017-08-01

    In this article we present the difference in thermal stability of Li/LiFePO4| half cells with liquid and solid polymer electrolytes. After two initial cycles, the cells were charged to two different state of charge (SOC) of 50 and 100%. The thermal stability of the half cells is assessed with an accelerating rate calorimeter, and the thermal runaway parameters are discussed for each experiment: dependence of self-heating rate on temperature, temperature of a first-detected exothermic reaction, and maximum cell temperature. The dependence of those parameters with respect to the SOC is also presented.

  13. Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Sakamoto, Y.; Ishii, Y.; Kawasaki, S.

    2016-07-01

    Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

  14. Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

    SciTech Connect

    Sakamoto, Y.; Ishii, Y.; Kawasaki, S.

    2016-07-06

    Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

  15. Solid state double layer capacitor based on a polyether polymer electrolyte blend and nanostructured carbon black electrode composites

    NASA Astrophysics Data System (ADS)

    Lavall, Rodrigo L.; Borges, Raquel S.; Calado, Hállen D. R.; Welter, Cezar; Trigueiro, João P. C.; Rieumont, Jacques; Neves, Bernardo R. A.; Silva, Glaura G.

    An all solid double layer capacitor was assembled by using poly(ethylene oxide)/poly(propylene glycol)- b-poly(ethylene glycol)- b-poly(propylene glycol)-bis(2-aminopropyl ether) blend (PEO-NPPP) and LiClO 4 as polymer electrolyte layer and PEO-NPPP-carbon black (CB) as electrode film. High molecular weight PEO and the block copolymer NPPP with molecular mass of 2000 Da were employed, which means that the design is safe from the point of view of solvent or plasticizer leakage and thus, a separator is not necessary. Highly conductive with large surface area nanostructured carbon black was dispersed in the polymer blend to produce the electrode composite. The electrolyte and electrode multilayers prepared by spray were studied by differential scanning calorimetry, atomic force microscopy (AFM) and impedance spectroscopy. The ionic conductivity as a function of temperature was fitted with the Williams-Landel-Ferry equation, which indicates a conductivity mechanism typical of solid polymer electrolyte. AFM images of the nanocomposite electrode showed carbon black particles of approximately 60 nm in size well distributed in a semicrystalline and porous polymer blend coating. The solid double layer capacitor with 10 wt.% CB was designed with final thickness of approximately 130 μm and delivered a capacitance of 17 F g -1 with a cyclability of more than 1000 cycles. These characteristics make possible the construction of a miniature device in complete solid state which will avoid electrolyte leakage and present a performance superior to other similar electric double layer capacitors (EDLCs) presented in literature, as assessed in specific capacitance by total carbon mass.

  16. Highly efficient solid-state dye-sensitized solar cells based on hexylimidazolium iodide ionic polymer electrolyte prepared by in situ low-temperature polymerization

    NASA Astrophysics Data System (ADS)

    Wang, Guiqiang; Yan, Chao; Zhang, Juan; Hou, Shuo; Zhang, Wei

    2017-03-01

    Solid-state dye-sensitized solar cells (DSCs) are fabricated using a novel ionic polymer electrolyte containing hexylimidazolium iodide (HII) ionic polymer prepared by in situ polymerization of N,N‧-bis(imidazolyl) hexane and 1,6-diiodohexane without an initiator at low temperature (40 °C). The as-prepared HII ionic polymer has a similar structure to alkylimidazolium iodide ionic liquid, and the imidazolium cations are contained in the polymer main chain; so, it can act simultaneously as the redox mediator in the electrolyte. By incorporating an appropriate amount of 1,3-dimethylimidazolium iodide (DMII) in HII ionic polymer (DMII/HII ionic polymer = 0.7:1, weight ratio), the conductivity of the ionic polymer electrolyte is greatly improved due to the formation of Grotthuss bond exchange. In addition, in situ synthesis of ionic polymer electrolyte guarantees a good pore-filling of the electrolyte in the TiO2 photoanode. As a result, the solid-state DSC based on the ionic polymer electrolyte containing HII ionic polymer and DMII without iodine achieves a conversion efficiency of 6.55% under the illumination of 100 mW cm-2 (AM 1.5), which also exhibits a good at-rest stability at room temperature.

  17. Graphene tailored polymer gel electrolytes for 9.1%-efficiency quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Zheng, Jingjing

    2017-04-01

    Pursuit of technological implementation with enhanced photoelectric conversion efficiency and power generation ability in the dark is a persistent objective for dye-sensitized solar cells (DSSCs). We launch here three strategies of designing graphene tailored polymer gel electrolytes (PGEs) with an electron-conducting feature, aiming at reserving I-/I3- redox couples into three-dimensional (3D) PGE framework, reducing I3- species within the PGE and shortening the diffusion length of redox couples. The 3D PGE provides framework for I-/I3- diffusion like in a liquid system, whereas graphene experiences to form interconnected channels along polyelectrolyte backbones. The results demonstrate that a power conversion efficiency of 9.1% is yielded on the resultant quasi-solid-state DSSCs by optimizing synthesis strategies.

  18. Effect of Molecular Weight on Mechanical and Electrochemical Performance of All Solid-State Polymer Electrolyte Membranes

    NASA Astrophysics Data System (ADS)

    He, Ruixuan; Ward, Daniel; Echeverri, Mauricio; Kyu, Thein

    2015-03-01

    Guided by ternary phase diagrams of polyethylene glycol diacrylate (PEGDA), succinonitrile plasticizer, and LiTFSI salt, completely amorphous solid-state transparent polymer electrolyte membranes (ss-PEM) were fabricated by UV irradiation in the isotropic melt state. Effects of PEGDA molecular weight (700 vs 6000 g/mol) on ss-PEM performance were investigated. These amorphous PEMs have superionic room temperature ionic conductivity of ~10-3 S/cm, whereby PEGDA6000-PEM outperforms its PEGDA700 counterpart, which may be ascribed to lower crosslinking density and greater segmental mobility. The longer chain between crosslinked points of PEGDA6000-PEM is responsible for greater extensibility of ~80% versus ~7% of PEGDA700-PEM. Besides, both PEMs exhibited thermal stability up to 120 °C and electrochemical stability versus Li+/Li up to 4.7V. LiFePO4/PEM/Li and Li4Ti5O12 /PEM/Li half-cells exhibited stable cyclic behavior up to 50 cycles tested with a capacity of ~140mAh/g, suggesting that LiFePO4/PEM/Li4Ti5O12 may be a promising full-cell for all solid-state lithium battery. We thank NSF-DMR 1161070 for providing funding of this project.

  19. Solid-state Mg/MnO 2 cell employing a gel polymer electrolyte of magnesium triflate

    NASA Astrophysics Data System (ADS)

    Kumar, G. Girish; Munichandraiah, N.

    In view of the abundant resources, low costs and the relatively low reactivity of magnesium, solid-state batteries using this metal are worthy of investigation in comparison with solid-state lithium batteries. For such cells, a gel polymer electrolyte (GPE) is prepared using polyacrylonitrile, propylene carbonate, ethylene carbonate and magnesium triflate. The composition of GPE is optimized in view of the minimum liquid components required for gel formation and maximum ionic conductivity. This is achieved by preparing several films with varying concentration of the constituents and measuring their ionic conductivity by AC impedance spectroscopy. Mg/GPE/MnO 2 cells are assembled and their discharge behaviour is studied. A capacity value of about 40 mA h per gram of MnO 2 is obtained. Cyclic voltammetric experiments demonstrate qualitatively the reversible behaviour of the MnO 2 electrode. The Mg/GPE/MnO 2 cells are subjected to about 20 charge-discharge cycles with a consistent capacity of about 20 mA h g -1. Cycle-life data is limited by surface passivation of the magnesium negative electrode and poor rechargeability of the MnO 2 positive electrode. At present, the results show that the Mg/GPE/MnO 2 cells have an inferior performance in comparison with that of well-developed, lithium-based rechargeable batteries. Further extensive investigations are required to raise the performance of the magnesium-based rechargeable cells to practical levels.

  20. 3-V Solid-State Flexible Supercapacitors with Ionic-Liquid-Based Polymer Gel Electrolyte for AC Line Filtering.

    PubMed

    Kang, Yu Jin; Yoo, Yongju; Kim, Woong

    2016-06-08

    State-of-the-art solid-state flexible supercapacitors with sufficiently fast response speed for AC line filtering application suffer from limited energy density. One of the main causes of the low energy density is the low cell voltage (1 V), which is limited by aqueous-solution-based gel electrolytes. In this work, we demonstrate for the first time a 3-V flexible supercapacitor for AC line filtering based on an ionic-liquid-based polymer gel electrolyte and carbon nanotube electrode material. The flexible supercapacitor exhibits an areal energy density that is more than 20 times higher than that of the previously demonstrated 1-V flexible supercapacitor (0.66 vs 0.03 μWh/cm(2)) while maintaining excellent capacitive behavior at 120 Hz. The supercapacitor shows a maximum areal power density of 1.5 W/cm(2) and a time constant of 1 ms. The improvement of the cell voltage while maintaining the fast-response capability greatly improves the potential of supercapacitors for high-frequency applications in wearable and/or portable electronics.

  1. Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

    2016-02-01

    The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

  2. Absorbency and conductivity of quasi-solid-state polymer electrolytes for dye-sensitized solar cells: A characterization review

    NASA Astrophysics Data System (ADS)

    Mohamad, Ahmad Azmin

    2016-10-01

    The application of quasi-solid state electrolytes for dye-sensitized solar cells opens up an interesting research field to explore, which is evident from the increasing amount of publications on this topic. Since 2010, significant progress has been made with new and more complicated quasi-solid-states materials being produced. The optimization of new materials requires specific characterizations. This review presents a comprehensive overview and recent progress of characterization methods for studying quasi-solid-state electrolytes. Emphasis is then placed on the absorbency and conductivity characterizations. Each characterization will be reviewed according to the objective, experimental set-up, summary of important outcomes, and a few case studies worth discussing. Finally, strategies for future characterizations and developments are described.

  3. A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

    PubMed

    Xia, Yan; Wang, Xiuli; Xia, Xinhui; Xu, Ruochen; Zhang, Shengzhao; Wu, Jianbo; Liang, Yanfei; Gu, Changdong; Tu, Jiangping

    2017-09-05

    Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li1.5 Al0.5 Ti1.5 (PO4 )3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g(-1) at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Solid Polymer Electrolytes Based on Functionalized Tannic Acids from Natural Resources for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Shim, Jimin; Bae, Ki Yoon; Kim, Hee Joong; Lee, Jin Hong; Kim, Dong-Gyun; Yoon, Woo Young; Lee, Jong-Chan

    2015-12-21

    Solid polymer electrolytes (SPEs) for all-solid-state lithium-ion batteries are prepared by simple one-pot polymerization induced by ultraviolet (UV) light using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as an ion-conducting monomeric unit and tannic acid (TA)-based crosslinking agent and plasticizer. The crosslinking agent and plasticizer based on natural resources are obtained from the reaction of TA with glycidyl methacrylate and glycidyl poly(ethylene glycol), respectively. Dimensionally stable free-standing SPE having a large ionic conductivity of 5.6×10(-4)  Scm(-1) at room temperature can be obtained by the polymerization of PEGMA into P(PEGMA) with a very small amount (0.1 wt %) of the crosslinking agent and 2.0 wt % of the plasticizer. The ionic conductivity value of SPE with a crosslinked structure is one order of magnitude larger than that of linear P(PEGMA) in the waxy state. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Novel solid-state polymer electrolyte consisting of a porous layer-by-layer polyelectrolyte thin film and oligoethylene glycol.

    PubMed

    Lowman, Geoffrey M; Tokuhisa, Hiroaki; Lutkenhaus, Jodie L; Hammond, Paula T

    2004-10-26

    A novel solid-state polymer electrolyte was constructed using layer-by-layer (LbL) polyelectrolyte assembly of linear poly(ethylenimine) (LPEI) and poly(acrylic acid) (PAA), combined with a plasticization step using oligoethylene glycol dicarboxylic acid (OEGDA). This composite film exhibits a relatively high ionic conductivity of 9.5 x 10(-5) S/cm at 25 degrees C and 22% relative humidity. Detailed characterization of the composite was undertaken using grazing-angle Fourier transform infrared (GA-FTIR), atomic force microscopy (AFM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and impedance spectroscopy. After immersing the LPEI/PAA films into OEGDA aqueous solutions, the films exhibited a swelling behavior and increased surface roughness indicative of porosity induced by reorganization of ionic interactions between LPEI and PAA in acidic solution. This internal porous structure allows inclusion of OEGDA within the multilayer and increased ionic conductivity under ambient conditions due to the combined effects of plasticization of the LbL matrix by atmospheric water as well as the added mobility of ions in molten OEGDA within the composite.

  6. Optimization of a quasi-solid-state dye-sensitized solar cell employing a nanocrystal-polymer composite electrolyte modified with water and ethanol.

    PubMed

    Yang, Ying; Zhou, Cong-Hua; Xu, Sheng; Zhang, Jing; Wu, Su-Juan; Hu, Hao; Chen, Bo-Lei; Tai, Qi-Dong; Sun, Zheng-Hua; Liu, Wei; Zhao, Xing-Zhong

    2009-03-11

    A quasi-solid-state dye-sensitized solar cell employing a poly(ethylene oxide)-poly(vinylidene fluoride) (PEO-PVDF)/TiO2 gel electrolyte modified by various concentrations of water and ethanol is described. It is shown that the introduction of water and ethanol prevents the crystallization of the polymer matrix, and enhances the free I(-)/I(3)(-) concentration and the networks for ion transportation in the electrolyte, thus leading to an improvement in conductivity. A high energy conversion efficiency of about 5.8% is achieved by controlling the additive concentration in the electrolyte. Optimization of the additive-modified electrolyte performance has been obtained by studying the cross-linking behavior of water and ethanol with Fourier transform infrared (FTIR), differential scanning calorimetry (DSC) and viscosity measurements, and the electrical conduction behavior of the electrolyte with impedance spectra measurements.

  7. Ultra-thin Solid-State Li-Ion Electrolyte Membrane Facilitated by a Self-Healing Polymer Matrix.

    PubMed

    Whiteley, Justin M; Taynton, Philip; Zhang, Wei; Lee, Se-Hee

    2015-11-18

    Thin solid membranes are formed by a new strategy, whereby an in situ derived self-healing polymer matrix that penetrates the void space of an inorganic solid is created. The concept is applied as a separator in an all-solid-state battery with an FeS2 -based cathode and achieves tremendous performance for over 200 cycles. Processing in dry conditions represents a paradigm shift for incorporating high active-material mass loadings into mixed-matrix membranes.

  8. Polymer composite electrolytes having core-shell silica fillers with anion-trapping boron moiety in the shell layer for all-solid-state lithium-ion batteries.

    PubMed

    Shim, Jimin; Kim, Dong-Gyun; Kim, Hee Joong; Lee, Jin Hong; Lee, Jong-Chan

    2015-04-15

    Core-shell silica particles with ion-conducting poly(ethylene glycol) and anion-trapping boron moiety in the shell layer were prepared to be used as fillers for polymer composite electrolytes based on organic/inorganic hybrid branched copolymer as polymer matrix for all-solid-state lithium-ion battery applications. The core-shell silica particles were found to improve mechanical strength and thermal stability of the polymer matrix and poly(ethylene glycol) and boron moiety in the shell layer increase compatibility between filler and polymer matrix. Furthermore, boron moiety in the shell layer increases both ionic conductivity and lithium transference number of the polymer matrix because lithium salt can be more easily dissociated by the anion-trapping boron. Interfacial compatibility with lithium metal anode is also improved because well-dispersed silica particles serve as protective layer against interfacial side reactions. As a result, all-solid-state battery performance was found to be enhanced when the copolymer having core-shell silica particles with the boron moiety was used as solid polymer electrolyte.

  9. Enhancement of monobasal solid-state dye-sensitized solar cells with polymer electrolyte assembling imidazolium iodide-functionalized silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Hu, Min; Sun, Jiazeng; Rong, Yaoguang; Yang, Ying; Liu, Linfeng; Li, Xiong; Forsyth, Maria; MacFarlane, Douglas R.; Han, Hongwei

    2014-02-01

    An alkyl imidazolium iodide-functionalized silica (SiO2-ImI)/PEO/PVDF nano-composite polymer electrolyte (CPE) is developed for the monobasal solid-state dye-sensitized solar cell (DSSC) based on a printable carbon counter electrode. The results indicate that the alkyl imidazolium iodide chemically engineered onto the surface of silica, and that the SiO2-ImI can be distributed more uniformly in the PEO/PVDF polymer matrix than bare SiO2 nanoparticles. Electrochemical impedance spectroscopy (EIS) tests reveal that the conductivity of SiO2-ImI CPE is greatly increased compared with pure polymer electrolyte or the bare SiO2 CPE. As a result, the highest ionic conductivity of 1.07 × 10-4 S cm-1 and a power conversion efficiency of 3.83% is obtained at AM 1.5 and 100 mW cm-2 with the 8 wt% SiO2-ImI CPE based monobasal solid-state DSSCs. Moreover, the preliminary stability tests indicate that SiO2-ImI CPE based monobasal solid-state DSSCs present better stability than bare SiO2 CPE devices.

  10. Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

    NASA Astrophysics Data System (ADS)

    Obeidat, Amr M.

    Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also

  11. A polymer gel electrolyte with an inverse opal structure and its effects on the performance of quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, Shuai; Dong, Gong-Yu; Lin, Bencai; Qu, Jie; Yuan, Ning-Yi; Ding, Jian-Ning

    2015-03-01

    To make the use of dye-sensitized solar cells (DSCs) practical, improvements in their light harvesting and power conversion efficiencies (PCEs) are needed. Hybrid polymer gels with an inverse opal structure (IOS) are prepared using various SiO2 opal films as templates and subsequent template etching. The polymer gel is further used as a host to prepare gel electrolytes with a photonic band gap (PBG), based on which quasi-solid-state DSCs are fabricated. The current-voltage curves indicate higher PCEs for the gel electrolytes with IOS than for reference gel electrolytes. A maximum average PCE of 3.85% is achieved for the gel electrolytes with a PBG around 690 nm, which is ca. 10% higher than the value for the reference gel electrolyte (3.48%). The action spectra reveal increases in the incident photo-to-current conversion efficiencies in and/or away the PBG region, indicating the significance of IOS for light-harvesting and PCE enhancement by back scattering and reflection of light. The electrochemical impedance spectra further demonstrate that the gel electrolytes with IOS have a lower Warburg impedance value than the reference gel electrolyte, which may also have contributed to the observed PCE enhancement. Besides, the IOS is found to give more stable performance of DSCs.

  12. Effective Infiltration of Gel Polymer Electrolyte into Silicon-Coated Vertically Aligned Carbon Nanofibers as Anodes for Solid-State Lithium-Ion Batteries.

    PubMed

    Pandey, Gaind P; Klankowski, Steven A; Li, Yonghui; Sun, Xiuzhi Susan; Wu, Judy; Rojeski, Ronald A; Li, Jun

    2015-09-23

    This study demonstrates the full infiltration of gel polymer electrolyte into silicon-coated vertically aligned carbon nanofibers (Si-VACNFs), a high-capacity 3D nanostructured anode, and the electrochemical characterization of its properties as an effective electrolyte/separator for future all-solid-state lithium-ion batteries. Two fabrication methods have been employed to form a stable interface between the gel polymer electrolyte and the Si-VACNF anode. In the first method, the drop-casted gel polymer electrolyte is able to fully infiltrate into the open space between the vertically aligned core-shell nanofibers and encapsulate/stabilize each individual nanofiber in the polymer matrix. The 3D nanostructured Si-VACNF anode shows a very high capacity of 3450 mAh g(-1) at C/10.5 (or 0.36 A g(-1)) rate and 1732 mAh g(-1) at 1C (or 3.8 A g(-1)) rate. In the second method, a preformed gel electrolyte film is sandwiched between an Si-VACNF electrode and a Li foil to form a half-cell. Most of the vertical core-shell nanofibers of the Si-VACNF anode are able to penetrate into the gel polymer film while retaining their structural integrity. The slightly lower capacity of 2800 mAh g(-1) at C/11 rate and ∼1070 mAh g(-1) at C/1.5 (or 2.6 A g(-1)) rate have been obtained, with almost no capacity fade for up to 100 cycles. Electrochemical impedance spectroscopy does not show noticeable changes after 110 cycles, further revealing the stable interface between the gel polymer electrolyte and the Si-VACNFs anode. These results show that the infiltrated flexible gel polymer electrolyte can effectively accommodate the stress/strain of the Si shell due to the large volume expansion/contraction during the charge-discharge processes, which is particularly useful for developing future flexible solid-state lithium-ion batteries incorporating Si-anodes.

  13. High performance solid-state supercapacitor with PVA-KOH-K3[Fe(CN)6] gel polymer as electrolyte and separator

    NASA Astrophysics Data System (ADS)

    Ma, Guofu; Li, Jiajia; Sun, Kanjun; Peng, Hui; Mu, Jingjing; Lei, Ziqiang

    2014-06-01

    A gel polymer PVA-KOH-K3[Fe(CN)6] is prepared by potassium hydroxide and potassium ferricyanide doped polyvinyl alcohol, and a solid-state supercapacitor is assembled using the gel polymer as electrolyte and separator, activated carbons as electrode. The gel polymer exhibits flexible, high ionic conductivity and wide potential properties. The electrochemical properties of the supercapacitor are investigated using cyclic voltammetry, galvanostatic charge/discharge, and impedance spectroscopy techniques. The electrode specific capacitance of the supercapacitor can be as high as 430.95 F g-1, and after 1000 cycles at a current density of 1 A g-1 it still remains higher than 380 F g-1. The energy density and power density of the supercapacitor reach 57.94 Wh kg-1 and 59.84 kW kg-1, respectively. These novel flexible gel polymers are desirable for applications in supercapacitor devices.

  14. Toward highly stable solid-state unconventional thin-film battery-supercapacitor hybrid devices: Interfacing vertical core-shell array electrodes with a gel polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Pandey, Gaind P.; Klankowski, Steven A.; Liu, Tao; Wu, Judy; Li, Jun

    2017-02-01

    A novel solid-state battery-supercapacitor hybrid device is fabricated for high-performance electrical energy storage using a Si anode and a TiO2 cathode in conjunction with a flexible, solid-like gel polymer electrolyte film as the electrolyte and separator. The electrodes were fabricated as three-dimensional nanostructured vertical arrays by sputtering active materials as conformal shells on vertically aligned carbon nanofibers (VACNFs) which serve as the current collector and structural template. Such nanostructured vertical core-shell array-electrodes enable short Li-ion diffusion path and large pseudocapacitive contribution by fast surface reactions, leading to the hybrid features of batteries and supercapacitors that can provide high specific energy over a wide range of power rates. Due to the improved mechanical stability of the infiltrated composite structure, the hybrid cell shows excellent cycling stability and is able to retain more than 95% of the original capacity after 3500 cycles. More importantly, this solid-state device can stably operate in a temperature range from -20 to 60 °C with a very low self-discharge rate and an excellent shelf life. This solid-state architecture is promising for the development of highly stable thin-film hybrid energy storage devices for unconventional applications requiring largely varied power, wider operation temperature, long shelf-life and higher safety standards.

  15. All-solid-state supercapacitors with poly(3,4-ethylenedioxythiophene)-coated carbon fiber paper electrodes and ionic liquid gel polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Pandey, G. P.; Rastogi, A. C.; Westgate, Charles R.

    2014-01-01

    All-solid-state thin supercapacitors have been fabricated using current pulse polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) over carbon fiber paper and ionic liquid based gel polymer electrolyte. The PEDOT-coated carbon paper electrodes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) which confirm the porous morphology of PEDOT at the nanoscale and a high degree of ClO4- dopant ion conjugation. The performance characteristics of the supercapacitor cells have been evaluated by ac impedance spectroscopy, cyclic voltammetry and galvanostatic charge-discharge techniques. The PEDOT electrode shows specific capacitance of ∼154.5 F g-1, which correspond to the cell area-normalized capacitance of 85 mF cm-2. The maximum specific energy and specific power of the solid-state supercapacitor cell, calculated from charge-discharge characteristics, are 6.5 Wh kg-1 and 11.3 kW kg-1, respectively. The solid-state supercapacitor shows good cycle durability and time stability. The thin, lightweight, gel electrolyte based supercapacitor shows considerable potential for low-cost, high-performance energy storage applications.

  16. Novel polymer gel electrolyte with organic solvents for quasi-solid-state dye-sensitized solar cells.

    PubMed

    Shen, Sheng-Yen; Dong, Rui-Xuan; Shih, Po-Ta; Ramamurthy, Vittal; Lin, Jiang-Jen; Ho, Kuo-Chuan

    2014-11-12

    A cross-linked copolymer was previously synthesized from poly(oxyethylene) diamine (POE-amine) and an aromatic anhydride and cured to generate an amide-imide cross-linking structure. The copolymer containing several chemical groups such as POE, amido acids, and imide, enabled to absorb liquid electrolytes in methoxypropionitrile (MPN) for suitable uses in dye-sensitized solar cells. To establish the advantages of polymer gel electrolytes (PGE), the same copolymer was studied by using different electrolyte solvents including propylene carbonate (PC), dimethylformamide, and N-methyl-2-pyrrolidone, and shown their long-term stability. The morphology of the copolymer after absorbing liquid electrolytes in these solvents was proven the same as a 3D interconnected nanochannels, evidenced field emission-scanning electron microscopy. Among these solvents, PC was selected as the optimized PGE, which demostrated a higher power conversion efficiency (8.31%) than that of the liquid electrolyte (7.89%). In particular, the long-term stability of only a 5% decrease in the cell efficiency after 1000 h of testing was achieved. It was proven the developed copolymer as PGE was versatile for different solvents showing high efficiency and long-term durability.

  17. A new solid polymer electrolyte incorporating Li10GeP2S12 into a polyethylene oxide matrix for all-solid-state lithium batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Yanran; Wu, Chuan; Peng, Gang; Chen, Xiaotian; Yao, Xiayin; Bai, Ying; Wu, Feng; Chen, Shaojie; Xu, Xiaoxiong

    2016-01-01

    Li10GeP2S12 (LGPS) is incorporated into polyethylene oxide (PEO) matrix to fabricate composite solid polymer electrolyte (SPE) membranes. The lithium ion conductivities of as-prepared composite membranes are evaluated, and the optimal composite membrane exhibits a maximum ionic conductivity of 1.21 × 10-3 S cm-1 at 80 °C and an electrochemical window of 0-5.7 V. The phase transition behaviors for electrolytes are characterized by DSC, and the possible reasons for their enhanced ionic conductivities are discussed. The LGPS microparticles, acting as active fillers incorporation into the PEO matrix, have a positive effect on the ionic conductivity, lithium ion transference number and electrochemical stabilities. In addition, two kinds of all-solid-state lithium batteries (LiFeO4/SPE/Li and LiCoO2/SPE/Li) are fabricated to demonstrate the good compatibility between this new SPE membrane and different electrodes. And the LiFePO4/Li battery exhibits fascinating electrochemical performance with high capacity retention (92.5% after 50 cycles at 60 °C) and attractive capacities of 158, 148, 138 and 99 mAh g-1 at current rates of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C, respectively. It is demonstrated that this new composite SPE should be a promising electrolyte applied in solid state batteries based on lithium metal electrode.

  18. High-energy-density, all-solid-state microsupercapacitors with three-dimensional interdigital electrodes of carbon/polymer electrolyte composite.

    PubMed

    Pu, Juan; Wang, Xiaohong; Zhang, Tianyi; Li, Siwei; Liu, Jinghe; Komvopoulos, Kyriakos

    2016-01-29

    Novel all-solid-state microsupercapacitors (MSCs) with three-dimensional (3D) electrodes consisting of active materials (i.e., graphene or activated carbon (AC) particles) and polymer electrolyte (PE) designed for high-energy-density storage applications were fabricated and tested in this work. The incorporation of PE in the electrode material enhances the accessibility of electrolyte ions to the surface of active materials and decreases the ion diffusion path during electrochemical charge/discharge. For a scan rate of 5 mV s(-1), the MSCs with graphene/PE and AC/PE composite electrodes demonstrate a very high areal capacitance of 95 and 134 mF cm(-2), respectively, comparable to that of 3D MSCs with liquid electrolyte. In addition, the graphene/PE MSCs show a ∼70% increase in specific capacitance after 10 000 charge/discharge cycles, attributed to an electro-activation process resulting from ion intercalation between the graphene nanosheets. The AC/PE MSCs also demonstrate excellent stability. The results of this study illustrate the potential of the present 3D MSCs for various high-density solid-state energy storage applications.

  19. Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers

    NASA Astrophysics Data System (ADS)

    Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

    2016-02-01

    We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180o.

  20. Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers

    PubMed Central

    Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

    2016-01-01

    We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180o. PMID:26846891

  1. Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers.

    PubMed

    Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

    2016-02-05

    We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180(°).

  2. Semi-interpenetrating solid polymer electrolyte based on thiol-ene cross-linker for all-solid-state lithium batteries

    NASA Astrophysics Data System (ADS)

    Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku

    2016-12-01

    We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.

  3. Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Hallinan, Daniel T.; Balsara, Nitash P.

    2013-07-01

    This review article covers applications in which polymer electrolytes are used: lithium batteries, fuel cells, and water desalination. The ideas of electrochemical potential, salt activity, and ion transport are presented in the context of these applications. Potential is defined, and we show how a cell potential measurement can be used to ascertain salt activity. The transport parameters needed to fully specify a binary electrolyte (salt + solvent) are presented. We define five fundamentally different types of homogeneous electrolytes: type I (classical liquid electrolytes), type II (gel electrolytes), type III (dry polymer electrolytes), type IV (dry single-ion-conducting polymer electrolytes), and type V (solvated single-ion-conducting polymer electrolytes). Typical values of transport parameters are provided for all types of electrolytes. Comparison among the values provides insight into the transport mechanisms occurring in polymer electrolytes. It is desirable to decouple the mechanical properties of polymer electrolyte membranes from the ionic conductivity. One way to accomplish this is through the development of microphase-separated polymers, wherein one of the microphases conducts ions while the other enhances the mechanical rigidity of the heterogeneous polymer electrolyte. We cover all three types of conducting polymer electrolyte phases (types III, IV, and V). We present a simple framework that relates the transport parameters of heterogeneous electrolytes to homogeneous analogs. We conclude by discussing electrochemical stability of electrolytes and the effects of water contamination because of their relevance to applications such as lithium ion batteries.

  4. Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

    PubMed

    Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

    2017-10-04

    We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10(-3) S cm(-1)) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g(-1) at 0.1 A g(-1)), better rate capability (64% capacity retention until 20 A g(-1)), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg(-1) at 1 A g(-1)) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

  5. Lithium-ion transport in inorganic solid state electrolyte

    NASA Astrophysics Data System (ADS)

    Jian, Gao; Yu-Sheng, Zhao; Si-Qi, Shi; Hong, Li

    2016-01-01

    An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and designing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell (to convey ions while isolate electrons), and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state electrolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes. Project supported by the National Natural Science Foundation of China (Grant No. 51372228), the Shanghai Pujiang Program, China (Grant No. 14PJ1403900), and the Shanghai Institute of Materials Genome from the Shanghai Municipal Science and Technology Commission, China (Grant No. 14DZ2261200).

  6. A zwitterionic gel electrolyte for efficient solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

    2016-05-01

    Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm-3 at 0.8 A cm-3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm-3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors.

  7. A zwitterionic gel electrolyte for efficient solid-state supercapacitors.

    PubMed

    Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

    2016-05-26

    Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm(-3) at 0.8 A cm(-3) with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm(-3), representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors.

  8. A zwitterionic gel electrolyte for efficient solid-state supercapacitors

    PubMed Central

    Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

    2016-01-01

    Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm−3 at 0.8 A cm−3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm−3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors. PMID:27225484

  9. High performance solid-state electric double layer capacitor from redox mediated gel polymer electrolyte and renewable tamarind fruit shell derived porous carbon.

    PubMed

    Senthilkumar, S T; Selvan, R Kalai; Melo, J S; Sanjeeviraja, C

    2013-11-13

    The activated carbon was derived from tamarind fruit shell and utilized as electrodes in a solid state electrochemical double layer capacitor (SSEDLC). The fabricated SSEDLC with PVA (polyvinyl alcohol)/H2SO4 gel electrolyte delivered high specific capacitance and energy density of 412 F g(-1) and 9.166 W h kg(-1), respectively, at 1.56 A g(-1). Subsequently, Na2MoO4 (sodium molybdate) added PVA/H2SO4 gel electrolyte was also prepared and applied for SSEDLC, to improve the performance. Surprisingly, 57.2% of specific capacitance (648 F g(-1)) and of energy density (14.4 Wh kg(-1)) was increased while introducing Na2MoO4 as the redox mediator in PVA/H2SO4 gel electrolyte. This improved performance is owed to the redox reaction between Mo(VI)/Mo(V) and Mo(VI)/Mo(IV) redox couples in Na2MoO4/PVA/H2SO4 gel electrolyte. Similarly, the fabricated device shows the excellent capacitance retention of 93% for over 3000 cycles. The present work suggests that the Na2MoO4 added PVA/H2SO4 gel is a potential electrolyte to improve the performance instead of pristine PVA/H2SO4 gel electrolyte. Based on the overall performance, it is strongly believed that the combination of tamarind fruit shell derived activated carbon and Na2MoO4/PVA/H2SO4 gel electrolyte is more attractive in the near future for high performance SSEDLCs.

  10. Solid-state polymer nanocomposite electrolyte of TiO2/PEO/NaClO4 for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Ni'mah, Yatim Lailun; Cheng, Ming-Yao; Cheng, Ju Hsiang; Rick, John; Hwang, Bing-Joe

    2015-03-01

    A free-standing transparent film for sodium-ion conduction in PEO-based solid polymer electrolyte (additionally comprising NaClO4 and nano-sized TiO2) has been fabricated for use in Na-ion batteries by using a solution casting technique. The crystallinity of the solid polymer electrolyte and the interactions between PEO and the Na-ions is characterized by X-ray diffraction (XRD) and Fourier transformed infra-red (FTIR) spectra, which reveals the degree of Na+ ion solvation by PEO oxygen atoms (EO:Na). The ionic conductivities of the films are investigated by impedance analysis from 1 MHz to 1 Hz within the temperature range 303-363 K. A solid polymer electrolyte with anatomic ratio EO:Na = 20 exhibits a maximum ionic conductivity of 1.35 × 10-4 S cm-1, which increases to 2.62 × 10-4 S cm-1 by the addition of TiO2 (3.4 nm, 5 wt%) at temperature 60 °C. The performance of a Na2/3Co2/3Mn1/3O2 half cell with a polymer electrolyte is compared to a similar cell with a liquid electrolyte.

  11. Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

    DOE PAGES

    Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.; ...

    2017-04-10

    Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiOtBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li2PO2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph of LiPON which closelymore » resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10-7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li+. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO2 as the cathode and Si as the anode operating at up to 1 mA/cm2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

  12. Lithium battery chemistries enabled by solid-state electrolytes

    NASA Astrophysics Data System (ADS)

    Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei

    2017-02-01

    Solid-state electrolytes are attracting increasing interest for electrochemical energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liquid or gaseous active materials (for example, lithium-air, lithium-sulfur and lithium-bromine systems). A low-cost, safe, aqueous electrochemical energy storage concept with a 'mediator-ion' solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic conductivity, electrochemical stability and mechanical properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.

  13. Solid polymer electrolytes

    DOEpatents

    Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

    1995-01-01

    This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

  14. Solid polymer electrolytes

    DOEpatents

    Abraham, K.M.; Alamgir, M.; Choe, H.S.

    1995-12-12

    This invention relates to Li ion (Li{sup +}) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF{sub 3}SO{sub 2}){sub 2}, LiAsF{sub 6}, and LiClO{sub 4}. 2 figs.

  15. Materials Development for All-Solid-State Battery Electrolytes

    NASA Astrophysics Data System (ADS)

    Wang, Weimin

    Solid electrolytes in all solid-state batteries, provide higher attainable energy density and improved safety. Ideal solid electrolytes require high ionic conductivity, a high elastic modulus to prevent dendrite growth, chemical compatibility with electrodes, and ease of fabrication into thin films. Although various materials types, including polymers, ceramics, and composites, are under intense investigation, unifying design principles have not been identified. In this thesis, we study the key ion transport mechanisms in relation to the structural characteristics of polymers and glassy solids, and apply derived material design strategies to develop polymer-silica hybrid materials with improved electrolyte performance characteristics. Poly(ethylene) oxide-based solid electrolytes containing ceramic nanoparticles are attractive alternatives to liquid electrolytes for high-energy density Li batteries. We compare the effect of Li1.3Al0.3Ti 1.7(PO4)3 active nanoparticles, passive TiO 2 nanoparticles and fumed silica. Up to two orders of magnitude enhancement in ionic conductivity is observed for composites with active nanoparticles, attributed to cation migration through a percolating interphase region that develops around the active nanoparticles, even at low nanoparticle loading. We investigate the structural origin of elastic properties and ionic migration mechanisms in sodium borosilicate and sodium borogermanate glass electrolyte system. A new statistical thermodynamic reaction equilibrium model is used in combination with data from nuclear magnetic resonance and Brillouin light scattering measurements to determine network structural unit fractions. The highly coordinated structural units are found to be predominantly responsible for effective mechanical load transmission, by establishing three-dimensional covalent connectivity. A strong correlation exists between bulk modulus and the activation energy for ion conduction. We describe the activated process in

  16. Highly Conductive Solid-State Hybrid Electrolytes Operating at Subzero Temperatures.

    PubMed

    Kwon, Taeyoung; Choi, Ilyoung; Park, Moon Jeong

    2017-07-19

    We report a unique, highly conductive, dendrite-inhibited, solid-state polymer electrolyte platform that demonstrates excellent battery performance at subzero temperatures. A design based on functionalized inorganic nanoparticles with interconnected mesopores that contain surface nitrile groups is the key to this development. Solid-state hybrid polymer electrolytes based on succinonitrile (SN) electrolytes and porous nanoparticles were fabricated via a simple UV-curing process. SN electrolytes were effectively confined within the mesopores. This stimulated favorable interactions with lithium ions, reduced leakage of SN electrolytes over time, and improved mechanical strength of membranes. Inhibition of lithium dendrite growth and improved electrochemical stability up to 5.2 V were also demonstrated. The hybrid electrolytes exhibited high ionic conductivities of 2 × 10(-3) S cm(-1) at room temperature and >10(-4) S cm(-1) at subzero temperatures, leading to stable and improved battery performance at subzero temperatures. Li cells made with lithium titanate anodes exhibited stable discharge capacities of 151 mAh g(-1) at temperatures below -10 °C. This corresponds to 92% of the capacity achieved at room temperature (164 mAh g(-1)). Our work represents a significant advance in solid-state polymer electrolyte technology and far exceeds the performance available with conventional polymeric battery separators.

  17. Quantifying the Solid State Charge Transport Characteristics of Radical Polymers

    NASA Astrophysics Data System (ADS)

    Baradwaj, Aditya; Rostro, Lizbeth; Boudouris, Bryan

    2014-03-01

    Radical polymers are an emerging class of functional macromolecules that have shown immense potential to transport charge in electrolyte-supported applications. However, quantifying the ability of these non-conjugated macromolecules to conduct charge has not been as well-studied in the solid state. Here, we present the characterization of the charge transport capability of a radical polymer, poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA) with well-defined molecular properties in the solid state. We show that charge transport occurs across the singularly occupied molecular orbital (SOMO) level of PTMA, and that this level is 5.2 eV removed from free vacuum. Additionally, we have measured the space-charge limited hole and electron mobility values of PTMA. We find that the mobility values of these radical polymers are of the same order (10-4 cm2 V-1 s-1) of many common conjugated polymers [ e . g . , poly(3-hexylthiophene) (P3HT)]. Furthermore, because the polymer backbone is non-conjugated, these macromolecules are extremely transparent. As such, we anticipate that radical polymers could become an important component of many transparent flexible electronic applications.

  18. Sulfide solid electrolyte with favorable mechanical property for all-solid-state lithium battery.

    PubMed

    Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2013-01-01

    All-solid-state secondary batteries that employ inorganic solid electrolytes are desirable because they are potentially safer than conventional batteries. The ionic conductivities of solid electrolytes are currently attracting great attention. In addition to the conductivity, the mechanical properties of solid electrolytes are important for improving the energy density and cycle performance. However, the mechanical properties of sulfide electrolytes have not been clarified in detail. Here, we demonstrate the unique mechanical properties of sulfide electrolytes. Sulfide electrolytes show room temperature pressure sintering. Ionic materials with low bond energies and a highly covalent character, which is promising for achieving a high ionic conductivity, tend to be suitable for room-temperature processing. The Young's moduli of sulfide electrolytes were measured to be about 20 GPa, which is an intermediate value between those of typical oxides and organic polymers.

  19. Sulfide Solid Electrolyte with Favorable Mechanical Property for All-Solid-State Lithium Battery

    PubMed Central

    Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2013-01-01

    All-solid-state secondary batteries that employ inorganic solid electrolytes are desirable because they are potentially safer than conventional batteries. The ionic conductivities of solid electrolytes are currently attracting great attention. In addition to the conductivity, the mechanical properties of solid electrolytes are important for improving the energy density and cycle performance. However, the mechanical properties of sulfide electrolytes have not been clarified in detail. Here, we demonstrate the unique mechanical properties of sulfide electrolytes. Sulfide electrolytes show room temperature pressure sintering. Ionic materials with low bond energies and a highly covalent character, which is promising for achieving a high ionic conductivity, tend to be suitable for room-temperature processing. The Young's moduli of sulfide electrolytes were measured to be about 20 GPa, which is an intermediate value between those of typical oxides and organic polymers. PMID:23877241

  20. In operando scanning electron microscopy and ultraviolet-visible spectroscopy studies of lithium/sulfur cells using all solid-state polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Marceau, Hugues; Kim, Chi-Su; Paolella, Andrea; Ladouceur, Sébastien; Lagacé, Marin; Chaker, Mohamed; Vijh, Ashok; Guerfi, Abdelbast; Julien, Christian M.; Mauger, Alain; Armand, Michel; Hovington, Pierre; Zaghib, Karim

    2016-07-01

    Lithium/solid polymer electrolyte (SPE)/sulfur cells were studied in operando by two techniques: Scanning Electron Microscope (SEM) and ultraviolet-visible absorption spectroscopy (UV-vis). During the operation of the cell, extensive polysulfide dissolution in the solid polymer electrolyte (cross-linked polyethylene oxide) leads to the formation of a catholyte. A clear micrograph of the thick passivation layer on the sulfur-rich anode and the decreased SPE thickness by cycling confirmed the failure mechanism; the capacity decays by reducing the amount of active material, and by contributing to a charge inhibiting mechanism called polysulfide shuttle. The formation of elemental sulfur is clearly visible in real time during the charge process beyond 2.3 V. The non-destructive in operando UV-vis study also shows the presence of characteristic absorption peaks evolving with cycling, demonstrating the accumulation of various polysulfide species, and the predominant formation of S42- and of S62- during discharge and charge, respectively. This finding implies that the charge and discharge reactions are not completely reversible and proceed along different pathways.

  1. Oxygen production using solid-state zirconia electrolyte technology

    NASA Technical Reports Server (NTRS)

    Suitor, Jerry W.; Clark, Douglas J.

    1991-01-01

    High purity oxygen is required for a number of scientific, medical, and industrial applications. Traditionally, these needs have been met by cryogenic distillation or pressure swing adsorption systems designed to separate oxygen from air. Oxygen separation from air via solid-state zirconia electrolyte technology offers an alternative to these methods. The technology has several advantages over the traditional methods, including reliability, compactness, quiet operation, high purity output, and low power consumption.

  2. Atomic Layer Deposited Lithium Silicates as Solid-State Electrolytes for All-Solid-State Batteries.

    PubMed

    Wang, Biqiong; Liu, Jian; Norouzi Banis, Mohammad; Sun, Qian; Zhao, Yang; Li, Ruying; Sham, Tsun-Kong; Sun, Xueliang

    2017-09-20

    Development of solid-state electrolyte (SSE) thin films is a key toward the fabrication of all-solid-state batteries (ASSBs). However, it is challenging for conventional deposition techniques to deposit uniform and conformal SSE thin films in a well-controlled fashion. In this study, atomic layer deposition (ALD) was used to fabricate lithium silicate thin films as a potential SSE for ASSBs. Lithium silicates thin films were deposited by combining ALD Li2O and SiO2 subcycles using lithium tert-butoxide, tetraethylorthosilane, and H2O as precursors. Uniform and self-limiting growth was achieved at temperatures between 225 and 300 °C. X-ray absorption spectroscopy analysis disclosed that the as-deposited lithium silicates were composed of SiO4 tetrahedron structure and lithium oxide as the network modifier. X-ray photoelectron spectroscopy confirmed the chemical states of Li in the thin films were the same with that in standard lithium silicate. With one to one subcycle of Li2O and SiO2 the thin films had a composition close to Li4SiO4 whereas one more subcycle of Li2O delivered a higher lithium content. The lithium silicate thin film prepared at 250 °C exhibited an ionic conductivity of 1.45× 10(-6) S cm(-1) at 373 K. The high ionic conductivity of lithium silicate was due to the higher lithium concentration and lower activation energy.

  3. An all-solid-state lithium ion battery electrolyte membrane fabricated by hot-pressing method

    NASA Astrophysics Data System (ADS)

    Han, Pengfei; Zhu, Yuewu; Liu, Jin

    2015-06-01

    A cross-linked polymer electrolyte membrane (SPE) was fabricated by a solvent-free hot-pressing method for all-solid-state lithium ion battery. The ionic conductivity of the electrolyte is 1.34 × 10-3 S cm-1 and the decomposition potential is 4.87 V at the ethylene oxide (EO):LiN(SO2CF3)2 (LiTFSI) molar ratio of 20:1 and 120 °C. TG-DSC results show that the SPE is thermally stable up to 230 °C in argon atmosphere. The assembled LiFePO4/SPE/Li all-solid-state battery can stably work in the temperature range of 80-140 °C. At 120 °C, the initial discharge capacity of the battery is 156.7 mAh g-1 at 1C which is close to the theoretical capacity of the cathode material, showing that the solvent-free filming method is low-cost and environment-friendly for solid polymer electrolyte and all-solid-state lithium ion battery.

  4. Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

    PubMed Central

    Hu, Qichao; Caputo, Antonio; Sadoway, Donald R.

    2013-01-01

    Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (<80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed. PMID:23963203

  5. Solid-state graft copolymer electrolytes for lithium battery applications.

    PubMed

    Hu, Qichao; Caputo, Antonio; Sadoway, Donald R

    2013-08-12

    Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (< 80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.

  6. Ultrahigh Mobility in Solution-Processed Solid-State Electrolyte-Gated Transistors.

    PubMed

    Nketia-Yawson, Benjamin; Kang, Seok-Ju; Tabi, Grace Dansoa; Perinot, Andrea; Caironi, Mario; Facchetti, Antonio; Noh, Yong-Young

    2017-04-01

    A new concept of a high-capacitance polymeric dielectric based on high-k polymer and ion gel blends is reported. This solid-state electrolyte gate insulator enables remarkable field-effect mobilities exceeding 10 cm(2) V(-1) s(-1) for common polymer and other semiconductor families at VG ≤ 2 V owing to high areal capacitance (>4 µF cm(-2) ) from combined polarization of CF interface dipoles and electrical-double-layer formation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. All-solid-state reference electrodes based on conducting polymers.

    PubMed

    Kisiel, Anna; Marcisz, Honorata; Michalska, Agata; Maksymiuk, Krzysztof

    2005-12-01

    A novel construction of solution free (pseudo)reference electrodes, compatible with all-solid-state potentiometric indicator electrodes, has been proposed. These electrodes use conducting polymers (CP): polypyrrole (PPy) or poly(3,4-ethylenedioxythiophene) (PEDOT). Two different arrangements have been tested: solely based on CP and those where the CP phase is covered with a poly(vinyl chloride) based outer membrane of tailored composition. The former arrangement was designed to suppress or compensate cation- and anion-exchange, using mobile perchlorate ions and poly(4-styrenesulfonate) or dodecylbenzenesulfonate anions as immobilized dopants. The following systems were used: (i) polypyrrole layers doped simultaneously by two kinds of anions, both mobile and immobilized in the polymer layer; (ii) bilayers of polypyrrole with anion exchanging inner layer and cation-exchanging outer layer; (iii) polypyrrole doped by surfactant dodecylbenzenesulfonate ions, which inhibit ion exchange on the polymer/solution interface. For the above systems, recorded potentials have been found to be practically independent of electrolyte concentration. The best results, profound stability of potentials, have been obtained for poly(3,4-ethylenedioxythiophene) or polypyrrole doped by poly(4-styrenesulfonate) anions covered by a poly(vinyl chloride) based membrane, containing both anion- and cation-exchangers as well as solid potassium chloride and silver chloride with metallic silver. Differently to the cases (i)-(iii) these electrodes are much less sensitive to the influence of redox and pH interferences. This arrangement has been also characterized using electrochemical impedance spectroscopy and chronopotentiometry.

  8. Solid State Electrolytes Prepared from PEO (360) Silanated Silica

    NASA Technical Reports Server (NTRS)

    Maitra, P.; Ding, J.; Liu, B.; Wunder, S. L.; Lin, H.-P.; Chua, D.; Salomon, M.

    2002-01-01

    All solid state composite electrolytes were prepared using fumed silica (SiO2) silanated with an oligomeric polyethylene oxide (PEO) silane containing 6-9 ethylene oxide repeat units, a PEO matrix and LiClO4 (8/1 O/Li). The PEO-silane covalently attached to the silica was amorphous, with a T(sub g) that increased from -90 C to -53 C after attachment. The conductivity of films prepared using the PEO-silanated silica increased to approx. 6 x 10(exp -5) S/cm at RT compared with approx. 1 x 10(-5) S/cm for films prepared with unsilanated SiO2.

  9. A Unique Hybrid Quasi-Solid-State Electrolyte for Li-O2 Batteries with Improved Cycle Life and Safety.

    PubMed

    Yi, Jin; Zhou, Haoshen

    2016-09-08

    In the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li-O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li-O2 batteries. To overcome this issue, rechargeable solid-state Li-O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi-solid-state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li-O2 batteries. The proposed rechargeable solid-state Li-O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi-solid-state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li-O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid-state electrolytes for Li-O2 batteries upon future application.

  10. Pressure-controlled motion of single polymers through solid-state nanopores

    PubMed Central

    Lu, Bo; Hoogerheide, David P.; Zhao, Qing; Zhang, Hengbin; Tang, Zhipeng; Yu, Dapeng; Golovchenko, Jene A.

    2013-01-01

    Voltage-biased solid-state nanopores are well established in their ability to detect and characterize single polymers, such as DNA, in electrolytes. The addition of a pressure gradient across the nanopore yields a second molecular driving force that provides new freedom for studying molecules in nanopores. In this work, we show that opposing pressure and voltage bias enables nanopores to detect and resolve very short DNA molecules, as well as to detect near-neutral polymers. PMID:23802688

  11. Study of Solid State Protonic Battery with Composite Solid Electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, K.; Ambekar, P.; Bhoga, S. S.; Tiwari, R. U.

    2002-12-01

    The performance of all solid-state battery fabricated using a protonic solid electrolyte in conjunction with different cathodes namely MnO2, PbO2 and V6O13 is studied systematically. Composite proton conducting solid electrolyte NaH2PO4:Na2HPO4 is prepared following chemical route. The proton transport number determined following both the coulometric and the emf technique are found approximately equal to unity. Particularly, the cells are tested under constant load and constant current drain conditions. Open circuit voltage of cell with MnO2, PbO2 and V6O13 cathodes is found 1.5, 1.8 and 2.22V, respectively. The short-circuit-current 1, 0.5, and 0.3mA, respectively is obtained. The complex impedance analyses of the cell before during and after the discharge are carried. The maximum current drain of the order of 200 μA is achieved.

  12. Novel Li[(CF3SO2)(n-C4F9SO2)N]-Based Polymer Electrolytes for Solid-State Lithium Batteries with Superior Electrochemical Performance.

    PubMed

    Ma, Qiang; Qi, Xingguo; Tong, Bo; Zheng, Yuheng; Feng, Wenfang; Nie, Jin; Hu, Yong-Sheng; Li, Hong; Huang, Xuejie; Chen, Liquan; Zhou, Zhibin

    2016-11-02

    Solid polymer electrolytes (SPEs) would be promising candidates for application in high-energy rechargeable lithium (Li) batteries to replace the conventional organic liquid electrolytes, in terms of the enhanced safety and excellent design flexibility. Herein, we first report novel perfluorinated sulfonimide salt-based SPEs, composed of lithium (trifluoromethanesulfonyl)(n-nonafluorobutanesulfonyl)imide (Li[(CF3SO2)(n-C4F9SO2)N], LiTNFSI) and poly(ethylene oxide) (PEO), which exhibit relatively efficient ionic conductivity (e.g., 1.04 × 10(-4) S cm(-1) at 60 °C and 3.69 × 10(-4) S cm(-1) at 90 °C) and enough thermal stability (>350 °C), for rechargeable Li batteries. More importantly, the LiTNFSI-based SPEs could not only deliver the excellent interfacial compatibility with electrodes (e.g., Li-metal anode, LiFePO4 and sulfur composite cathodes), but also afford good cycling performances for the Li|LiFePO4 (>300 cycles at 1C) and Li-S cells (>500 cycles at 0.5C), in comparison with the conventional LiTFSI (Li[(CF3SO2)2N])-based SPEs. The interfacial impedance and morphology of the cycled Li-metal electrodes are also comparatively analyzed by electrochemical impedance spectra and scanning electron microscopy, respectively. These indicate that the LiTNFSI-based SPEs would be potential alternatives for application in high-energy solid-state Li batteries.

  13. Fabrication and characterization of solid-state, conducting polymer actuators

    SciTech Connect

    Xie, J.; Sansinena, J. M.; Gao, J.; Wang, H. L.

    2004-01-01

    We report here the fabrication and characterization of solid-state, conducting polymer actuators. The electrochemical activity of polyaniline (PANI) thin film coated with solid-state polyelectrolyte is very similar to the polyaniline thin film in an aqueous solution. The solid-state actuator is adhere to a lever arm of an force transducer and the force generation is measured in real time. The force generated by the actuator is found to be length dependent. However, the overall torques generated by the actuators with different lengths remains essentially the same. The effect of stimulation signals such as voltage, current, on the bending angle and displacement is also studied using square wave potential.

  14. Nanoporous polymer electrolyte

    DOEpatents

    Elliott, Brian [Wheat Ridge, CO; Nguyen, Vinh [Wheat Ridge, CO

    2012-04-24

    A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0.times.10.sup.-6 S/cm at 25.degree. C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

  15. New Polymer Electrolyte Cell Systems

    NASA Technical Reports Server (NTRS)

    Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.

    2004-01-01

    PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

  16. Atomic layer deposition of lithium phosphates as solid-state electrolytes for all-solid-state microbatteries.

    PubMed

    Wang, Biqiong; Liu, Jian; Sun, Qian; Li, Ruying; Sham, Tsun-Kong; Sun, Xueliang

    2014-12-19

    Atomic layer deposition (ALD) has been shown as a powerful technique to build three-dimensional (3D) all-solid-state microbattery, because of its unique advantages in fabricating uniform and pinhole-free thin films in 3D structures. The development of solid-state electrolyte by ALD is a crucial step to achieve the fabrication of 3D all-solid-state microbattery by ALD. In this work, lithium phosphate solid-state electrolytes were grown by ALD at four different temperatures (250, 275, 300, and 325 °C) using two precursors (lithium tert-butoxide and trimethylphosphate). A linear dependence of film thickness on ALD cycle number was observed and uniform growth was achieved at all four temperatures. The growth rate was 0.57, 0.66, 0.69, and 0.72 Å/cycle at deposition temperatures of 250, 275, 300, and 325 °C, respectively. Furthermore, x-ray photoelectron spectroscopy confirmed the compositions and chemical structures of lithium phosphates deposited by ALD. Moreover, the lithium phosphate thin films deposited at 300 °C presented the highest ionic conductivity of 1.73 × 10(-8) S cm(-1) at 323 K with ~ 0.51 eV activation energy based on the electrochemical impedance spectroscopy. The ionic conductivity was calculated to be 3.3 × 10(-8) S cm(-1) at 26 °C (299 K).

  17. Atomic layer deposition of lithium phosphates as solid-state electrolytes for all-solid-state microbatteries

    NASA Astrophysics Data System (ADS)

    Wang, Biqiong; Liu, Jian; Sun, Qian; Li, Ruying; Sham, Tsun-Kong; Sun, Xueliang

    2014-12-01

    Atomic layer deposition (ALD) has been shown as a powerful technique to build three-dimensional (3D) all-solid-state microbattery, because of its unique advantages in fabricating uniform and pinhole-free thin films in 3D structures. The development of solid-state electrolyte by ALD is a crucial step to achieve the fabrication of 3D all-solid-state microbattery by ALD. In this work, lithium phosphate solid-state electrolytes were grown by ALD at four different temperatures (250, 275, 300, and 325 °C) using two precursors (lithium tert-butoxide and trimethylphosphate). A linear dependence of film thickness on ALD cycle number was observed and uniform growth was achieved at all four temperatures. The growth rate was 0.57, 0.66, 0.69, and 0.72 Å/cycle at deposition temperatures of 250, 275, 300, and 325 °C, respectively. Furthermore, x-ray photoelectron spectroscopy confirmed the compositions and chemical structures of lithium phosphates deposited by ALD. Moreover, the lithium phosphate thin films deposited at 300 °C presented the highest ionic conductivity of 1.73 × 10-8 S cm-1 at 323 K with ˜0.51 eV activation energy based on the electrochemical impedance spectroscopy. The ionic conductivity was calculated to be 3.3 × 10-8 S cm-1 at 26 °C (299 K).

  18. Solid-state dye-sensitized solar cells using polymerized ionic liquid electrolyte with platinum-free counter electrode.

    PubMed

    Kawano, Ryuji; Katakabe, Toru; Shimosawa, Hironobu; Nazeeruddin, Md Khaja; Grätzel, Michael; Matsui, Hiroshi; Kitamura, Takayuki; Tanabe, Nobuo; Watanabe, Masayoshi

    2010-02-28

    A polymerized ionic liquid electrolyte and platinum-free counter electrode are employed for solid-state DSSCs. We are able to prepare a thin polymer electrolyte layer on nanocrystalline TiO(2) in order to reduce the cell resistance. In addition, an electron conductive polymer (PEDOT/PSS) or a single-wall carbon nanotube gel is used with the cell as an inexpensive counter electrode instead of platinum. The overall photon-to-current conversion efficiency was 3.7% in this study.

  19. Fabrication and characterization of solid state conducting polymer actuators

    NASA Astrophysics Data System (ADS)

    Xie, Jian; Sansinena, Jose-Maria; Gao, Junbo; Wang, Hsing-Lin

    2004-07-01

    We report here the fabrication and characterization of solid-state conducting polymer actuators. The electrochemical activity of polyaniline (PANI) thin film coated with solid-state polyelectrolyte is very similar to the polyaniline thin film in an aqueous solution. The solid-state actuator is adhered to a lever arm of a force transducer and the force generation is measured in real time. The force generated by the actuator is found to be length dependent. However, the overall torque generated by the actuators with different lengths remains essentially the same. The effect of stimulation signals such as voltage, and current, on the bending angle and displacement is also studied using square wave potential.

  20. Magnetic field processed solid-state dye-sensitized solar cells with nickel oxide modified agarose electrolyte

    NASA Astrophysics Data System (ADS)

    Yang, Ying; Yi, Pengfei; Zhou, Conghua; Cui, Jiarui; Zheng, Xiaolu; Xiao, Si; Guo, Xueyi; Wang, Wenyong

    2013-12-01

    In this work we investigate novel, agarose-based polymer electrolyte that is modified by magnetic NiO nanoparticles for solid-state dye-sensitized solar cells (DSSCs) applications. After proper treatment under an external magnetic field, the agarose electrolyte exhibits increased ionic conductivity and better penetration into the mesoporous TiO2 photoanode film, which improves the power conversion efficiency of the DSSCs. Electrochemical impedance spectroscopy measurement is also performed to analyze the magnetic field effect on cell performance. After applying proper magnetic filed intensity, the recombination resistance and redox transport resistance in the devices are improved. This method can be possibly applied to other solid-state electrolyte materials to improve their performance and can lead to more efficient DSSCs.

  1. Solid polymer electrolyte compositions

    DOEpatents

    Garbe, James E.; Atanasoski, Radoslav; Hamrock, Steven J.; Le, Dinh Ba

    2001-01-01

    An electrolyte composition is featured that includes a solid, ionically conductive polymer, organically modified oxide particles that include organic groups covalently bonded to the oxide particles, and an alkali metal salt. The electrolyte composition is free of lithiated zeolite. The invention also features cells that incorporate the electrolyte composition.

  2. A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries

    PubMed Central

    Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

    2016-01-01

    Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm−1 at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface. PMID:27146645

  3. A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries.

    PubMed

    Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

    2016-05-05

    Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm(-1) at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface.

  4. A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

    2016-05-01

    Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm‑1 at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface.

  5. Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

    PubMed

    Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

    2016-01-11

    The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries.

  6. Electrochromic Device with Polymer Electrolyte

    NASA Astrophysics Data System (ADS)

    Solovyev, Andrey A.; Zakharov, Alexander N.; Rabotkin, Sergey V.; Kovsharov, Nikolay F.

    2016-08-01

    In this study a solid-state electrochromic device (ECD) comprised of a WO3 and Prussian blue (Fe4[Fe(CN)6]3) thin film couple with a Li+-conducting solid polymer electrolyte is discussed. WO3 was deposited on K-Glass substrate by magnetron sputtering method, while Prussian blue layer was formed on the same substrate by electrodeposition method. The parameters of the electrochromic device K-Glass/WO3/Li+-electrolyte/PB/K-Glass, such as change of transmittance, response time and stability were successfully tested using coupled optoelectrochemical methods. The device was colored or bleached by the application of +2 V or -2 V, respectively. Light modulation with transmittance variation of up to 59% and coloration efficiency of 43 cm2/C at a wavelength of 550 nm were obtained. Numerous switching of the ECD over 1200 cycles without the observation of significant degradation has been demonstrated.

  7. Ionically conducting PVA-LiClO4 gel electrolyte for high performance flexible solid state supercapacitors.

    PubMed

    Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Lokhande, Chandrakant D

    2015-12-15

    The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days. Copyright © 2015 Elsevier Inc. All rights reserved.

  8. Graphene quantum dots as the electrolyte for solid state supercapacitors

    PubMed Central

    Zhang, Su; Li, Yutong; Song, Huaihe; Chen, Xiaohong; Zhou, Jisheng; Hong, Song; Huang, Minglu

    2016-01-01

    We propose that graphene quantum dots (GQDs) with a sufficient number of acidic oxygen-bearing functional groups such as -COOH and -OH can serve as solution- and solid- type electrolytes for supercapacitors. Moreover, we found that the ionic conductivity and ion-donating ability of the GQDs could be markedly improved by simply neutralizing their acidic functional groups by using KOH. These neutralized GQDs as the solution- or solid-type electrolytes greatly enhanced the capacitive performance and rate capability of the supercapacitors. The reason for the enhancement can be ascribed to the fully ionization of the weak acidic oxygen-bearing functional groups after neutralization. PMID:26763275

  9. Composite Electrolyte for All-Solid-State Lithium Batteries: Low-Temperature Fabrication and Conductivity Enhancement.

    PubMed

    Lee, Sang-Don; Jung, Kyu-Nam; Kim, Hyeongil; Shin, Hyun-Seop; Song, Seung-Wan; Park, Min-Sik; Lee, Jong-Won

    2017-03-20

    All-solid-state lithium batteries offer notable advantages over conventional Li-ion batteries with liquid electrolytes in terms of energy density, stability, and safety. To realize this technology, it is critical to develop highly reliable solid-state inorganic electrolytes with high ionic conductivities and adequate processability. Li1+x Alx Ti2-x (PO4 )3 (LATP) with a NASICON (Na superionic conductor)-like structure is regarded as a potential solid electrolyte, owing to its high "bulk" conductivity (ca. 10(-3)  S cm(-1) ) and excellent stability against air and moisture. However, the solid LATP electrolyte still suffers from a low "total" conductivity, mainly owing to the blocking effect of grain boundaries to Li(+) conduction. In this study, an LATP-Bi2 O3 composite solid electrolyte shows very high total conductivity (9.4×10(-4)  S cm(-1) ) at room temperature. Bi2 O3 acts as a microstructural modifier to effectively reduce the fabrication temperature of the electrolyte and to enhance its ionic conductivity. Bi2 O3 promotes the densification of the LATP electrolyte, thereby improving its structural integrity, and at the same time, it facilitates Li(+) conduction, leading to reduced grain-boundary resistance. The feasibility of the LATP-Bi2 O3 composite electrolyte in all-solid-state Li batteries is also examined in this study.

  10. Solid-State Electrolyte-Gated Graphene in Optical Modulators.

    PubMed

    Rodriguez, Francisco J; Aznakayeva, Diana E; Marshall, Owen P; Kravets, Vasyl G; Grigorenko, Alexander N

    2017-05-01

    The gate-tunable wide-band absorption of graphene makes it suitable for light modulation from terahertz to visible light. The realization of graphene-based modulators, however, faces challenges connected with graphene's low absorption and the high electric fields necessary to change graphene's optical conductivity. Here, a solid-state supercapacitor effect with the high-k dielectric hafnium oxide is demonstrated that allows modulation from the near-infrared to shorter wavelengths close to the visible spectrum with remarkably low voltages (≈3 V). The electroabsorption modulators are based on a Fabry-Perot-resonator geometry that allows modulation depths over 30% for free-space beams. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. A Plastic-Crystal Electrolyte Interphase for All-Solid-State Sodium Batteries.

    PubMed

    Gao, Hongcai; Xue, Leigang; Xin, Sen; Park, Kyusung; Goodenough, John B

    2017-05-08

    The development of all-solid-state rechargeable batteries is plagued by a large interfacial resistance between a solid cathode and a solid electrolyte that increases with each charge-discharge cycle. The introduction of a plastic-crystal electrolyte interphase between a solid electrolyte and solid cathode particles reduces the interfacial resistance, increases the cycle life, and allows a high rate performance. Comparison of solid-state sodium cells with 1) solid electrolyte Na3 Zr2 (Si2 PO4 ) particles versus 2) plastic-crystal electrolyte in the cathode composites shows that the former suffers from a huge irreversible capacity loss on cycling whereas the latter exhibits a dramatically improved electrochemical performance with retention of capacity for over 100 cycles and cycling at 5 C rate. The application of a plastic-crystal electrolyte interphase between a solid electrolyte and a solid cathode may be extended to other all-solid-state battery cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. All solid-state redox supercapacitors based on supramolecular 1,5-diaminoanthraquinone oligomeric electrode and polymeric electrolytes

    NASA Astrophysics Data System (ADS)

    Hashmi, S. A.; Suematsu, Shunzo; Naoi, Katsuhiko

    Supramolecular conducting oligomeric 1,5-diaminoanthraquinone (DAAQ)-based all solid-state redox supercapacitors have been fabricated with the solid polymer electrolyte, poly vinyl alcohol (PVA)-H 3PO 4 blend and polymeric gel electrolyte poly methyl methacrylate (PMMA)-ethylene carbonate (EC)-propylene carbonate (PC)-tetra ethyl ammonium perchlorate (TEAClO 4) system. The films of gel electrolyte of the optimized composition PMMA (35 wt.%)-EC:PC (1:1 v/v)-1 M TEAClO 4 and polymer electrolyte PVA-H 3PO 4 (50:50 w/w) blend exhibited high ionic conductivity (10 -4 to 10 -3 S cm -1 at room temperature) with good mechanical strength, suitable for application in electrochemical supercapacitors. The capacitors have been characterized using a.c. impedance spectroscopy, linear sweep voltammetry and prolonged cyclic test. The maximum capacitance value of 3.7-5.4 mF cm -2 (equivalent to single electrode capacitance 125-184 F g -1 of DAAQ electrode) has been observed for the PMMA-gel electrolyte based capacitor. This corresponds to the energy density 92-135 Wh kg -1. System based on the proton-conducting PVA-H 3PO 4 polymer blend, however has relatively lower capacitance of 1.1-4.0 mF cm -2 (equivalent to single electrode capacitance of 36-136 F g -1).

  13. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    NASA Astrophysics Data System (ADS)

    Teran, Alexander Andrew

    -like environment around the ion while the second mechanism of ion conduction is attributed to diffusion of the entire polymer chain with coordinated ions. Equilibrated block copolymer electrolytes exhibit a non-monotonic dependence on molecular weight, decreasing with increasing molecular weight in the small molecular weight limit before increasing when molecular weight exceeds about 10 kg mol-1. Conductivity in annealed electrolytes was shown to be affected by two competing factors: the glass transition temperature of the insulating polystyrene block and the width of the conducting poly(ethylene oxide) (PEO) channel. In the low molecular weight limit, all ions are in contact with both polystyrene (PS) and PEO segments. The intermixing between PS and PEO segments is restricted to an interfacial zone of width of about 5 nm. The fraction of ions affected by the interfacial zone decreases as the conducting channel width increases. Furthermore, the effect of thermal history on the conductivity of the block copolymer electrolytes was examined. Results suggest that long-range order impedes ion transport, and consequently decreases in conductivity of up to 80% were seen upon annealing. The effect of morphology on ion transport was studied by conducting simultaneous impedance and X-ray scattering experiments as the block copolymer electrolyte transitioned from an ordered lamellar structure to a disordered phase. The ionic conductivity increased discontinuously through the transition from order to disorder. A simple framework for quantifying the magnitude of the discontinuity was presented. Finally, block copolymer electrolytes were examined specifically for use in high energy density solid state lithium/sulfur batteries. Such materials have been shown to form a stable interface with lithium metal anodes, maintain intimate contact upon cycling, and have sufficiently high shear moduli to retard dendrite formation. Having previously satisfied the concerns associated with the lithium metal

  14. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    NASA Astrophysics Data System (ADS)

    Kartini, Evvy; Manawan, Maykel

    2016-02-01

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say "the most important emerging energy technology" is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner's cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  15. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    SciTech Connect

    Kartini, Evvy; Manawan, Maykel

    2016-02-08

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  16. Conducting gel electrolytes with microporous structures for efficient quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Yuan, Shuangshuang; Tang, Qunwei; He, Benlin; Yu, Liangmin

    2015-01-01

    Conducting gel electrolytes from poly(acrylic acid)-cetyltrimethylammonium bromide/polyaniline (PAA-CTAB/PANi) and poly(acrylic acid)-cetyltrimethylammonium bromide/polypyrrole (PAA-CTAB/PPy) are synthesized under driving forces of both osmotic pressure and capillary force within microporous PAA-CTAB matrix. The as-synthesized PAA-CTAB/PANi or PAA-CTAB/PPy can extend the reduction reaction of triiodides from gel electrolyte/Pt counter electrode interface to both interface and three-dimensional framework of conducting gel electrolyte due to the electrical conduction of PANi or PPy toward reflux electrons (electrons from external circuit to Pt counter electrode). The enhanced kinetics for triiodides → iodide conversion is promising in elevating photovoltaic performances of quasi-solid-state dye-sensitized solar cells (DSSCs). Driving forces by both osmotic pressure across PAA-CTAB matrix and capillary force presenting in micropores can elevate the loading of PANi or PPy incorporated liquid electrolyte in per unit volume, leading to further enhancement in charge transfer and electrocatalytic activity. The total power conversion efficiencies of 7.11% and 6.39% are recorded in the solar cells with PAA-CTAB/PANi and PAA-CTAB/PPy electrolytes under one sun irradiation, respectively, whereas it is 6.07% for the cell device with pure PAA-CTAB gel electrolyte. Electrical and electrochemical characterizations reveal that the electrical conduction and electrocatalytic performances have been significantly enhanced by incorporating electrical conducting PANi or PPy into microporous PAA-CTAB matrix. The concept opens a new approach of fabricating efficient polymer gel electrolytes for robust quasi-solid-state DSSC applications.

  17. Investigation of solid state electrolyte silver-zinc battery

    NASA Technical Reports Server (NTRS)

    1970-01-01

    Study of the solid electrolyte ZnCl2-2NH3 rechargeable silver zinc electrochemical cell by X-ray diffraction analysis of the reaction products led to the conclusion that some water is consumed when the cell is discharged. Replacement of ZnCl2-2NH3 by ZnCl2-4Zn(OH)2 gave cells with high internal resistance and limited capacity. The salt formed by exposing a fibrous membrane saturated with ZnCl2 solution to fumes from ammonium carbonate in a dry desiccator comprised ZnCl2-4Zn(OH)2, ZnCl2,3NH4Cl and a third unidentified component. The temperature coefficient of open circuit EMF was nearly zero over the range from -25 C to 50 C. The internal resistance and polarization increased substantially below -25 C. There is some indication that exposure to 50 C for 29 hours causes some deterioration.

  18. Solidified inorganic-organic hybrid electrolyte for all solid state flexible lithium battery

    NASA Astrophysics Data System (ADS)

    Baek, Seung-Wook; Honma, Itaru; Kim, Jedeok; Rangappa, Dinesh

    2017-03-01

    Solidified lithium conducting hybrid electrolyte is designed and processed to realize the large scale and flexible solid state Li battery satisfying energy capability and safety issue. This paper presents a solidified inorganic-organic hybrid electrolyte to obtain commercially-acceptable ionic conductivity and a stable electrochemical window to prevent electrolyte decomposition in Li ion batteries. Li3PO4 coated with solidified [Li][EMI][TFSI] ionic liquid is developed as hybrid electrolyte material. The material has high electrochemical stability on a high-voltage cathode and metallic anode, and the solid electrolyte has high ionic conductivity. This Li3PO4-[Li][EMI][TFSI] hybrid electrolyte has the advantages of long-term operation, safety and flexibility, so it may be suitable for use in high-voltage cathodes and Li anode.

  19. All-Solid-State Textile Batteries Made from Nano-Emulsion Conducting Polymer Inks for Wearable Electronics

    PubMed Central

    Wei, Di; Cotton, Darryl; Ryhänen, Tapani

    2012-01-01

    A rollable and all-solid-state textile lithium battery based on fabric matrix and polymer electrolyte that allows flexibility and fast-charging capability is reported. When immerged into poly(3,4-ethylenedioxythiophene) (PEDOT) nano-emulsion inks, an insulating fabric is converted into a conductive battery electrode for a fully solid state lithium battery with the highest specific energy capacity of 68 mAh/g. This is superior to most of the solid-state conducting polymer primary and/or secondary batteries reported. The bending radius of such a textile battery is less than 1.5 mm while lightening up an LED. This new material combination and inherent flexibility is well suited to provide an energy source for future wearable and woven electronics. PMID:28348307

  20. Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

    NASA Technical Reports Server (NTRS)

    DeSilva, J .H. S. R.; Udinwe, V.; Sideris, P. J.; Smart, M. C.; Krause, F. C.; Hwang, C.; Smith, K. A.; Greenbaum, S. G.

    2012-01-01

    Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

  1. Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

    NASA Technical Reports Server (NTRS)

    DeSilva, J .H. S. R.; Udinwe, V.; Sideris, P. J.; Smart, M. C.; Krause, F. C.; Hwang, C.; Smith, K. A.; Greenbaum, S. G.

    2012-01-01

    Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

  2. New Solid Polymer Electrolytes for Improved Lithium Batteries

    NASA Technical Reports Server (NTRS)

    Hehemann, David G.

    2002-01-01

    The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

  3. Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction.

    PubMed

    Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis; Chang, Hao-Hsun; Pour, Nir; Lux, Simon F; Paschos, Odysseas; Maglia, Filippo; Lupart, Saskia; Lamp, Peter; Giordano, Livia; Shao-Horn, Yang

    2016-01-13

    This Review is focused on ion-transport mechanisms and fundamental properties of solid-state electrolytes to be used in electrochemical energy-storage systems. Properties of the migrating species significantly affecting diffusion, including the valency and ionic radius, are discussed. The natures of the ligand and metal composing the skeleton of the host framework are analyzed and shown to have large impacts on the performance of solid-state electrolytes. A comprehensive identification of the candidate migrating species and structures is carried out. Not only the bulk properties of the conductors are explored, but the concept of tuning the conductivity through interfacial effects-specifically controlling grain boundaries and strain at the interfaces-is introduced. High-frequency dielectric constants and frequencies of low-energy optical phonons are shown as examples of properties that correlate with activation energy across many classes of ionic conductors. Experimental studies and theoretical results are discussed in parallel to give a pathway for further improvement of solid-state electrolytes. Through this discussion, the present Review aims to provide insight into the physical parameters affecting the diffusion process, to allow for more efficient and target-oriented research on improving solid-state ion conductors.

  4. One-pot preparation of new copolymer electrolytes with tunable network structure for all-solid-state lithium battery

    NASA Astrophysics Data System (ADS)

    Chen, Bo; Xu, Qiang; Huang, Zhen; Zhao, Yanran; Chen, Shaojie; Xu, Xiaoxiong

    2016-11-01

    A new class of copolymer electrolytes with tunable network structure is successfully designed and prepared via a facile one-pot reaction. The trimethylolpropane triglycidyl ether (TMPEG) is cross-linked with poly (ethylene glycol) diamine (NPEG) to create well-defined solid network polymer electrolyte (SNPE). The network structure could be tuned by changing the molar ratio of TMPEG and NPEG or the molecular weight of NPEG. The effects of molecular weight of NPEG and molar ratio of EO/Li+ on the ionic conductivity are systematically investigated. The optimal electrolyte TMPEG-NPEG4K[2:1]-16:1 presents a maximum conductivity of 1.10 × 10-4 S cm-1 under 30 °C, and an 18-fold ionic conductivity enhancement in that of PEO-based electrolyte. Furthermore, it also exhibits wide electrochemical window (0-5.4 V), excellent compatibility with metallic Li, and superior mechanical properties. The all-solid-state lithium batteries LiFePO4/Li are assembled with TMPEG-NPEG4K[2:1]-16:1 electrolyte, and present good cycling and rate performance under 60 °C. The initial discharge specific capacities of the batteries are 161.7 mAh g-1 at 0.2 C and 132.7 mAh g-1 at 1 C, and the capacity retention ratio can be retained at 90.6% and 90.5% after 100 cycles. This new copolymer electrolyte may become a promising candidate for applications in all-solid-state lithium battery.

  5. Gel polymer electrolytes for batteries

    DOEpatents

    Balsara, Nitash Pervez; Eitouni, Hany Basam; Gur, Ilan; Singh, Mohit; Hudson, William

    2014-11-18

    Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at 25.degree. C.

  6. Ionic conductivity in crystalline polymer electrolytes.

    PubMed

    Gadjourova, Z; Andreev, Y G; Tunstall, D P; Bruce, P G

    2001-08-02

    Polymer electrolytes are the subject of intensive study, in part because of their potential use as the electrolyte in all-solid-state rechargeable lithium batteries. These materials are formed by dissolving a salt (for example LiI) in a solid host polymer such as poly(ethylene oxide) (refs 2, 3, 4, 5, 6), and may be prepared as both crystalline and amorphous phases. Conductivity in polymer electrolytes has long been viewed as confined to the amorphous phase above the glass transition temperature, Tg, where polymer chain motion creates a dynamic, disordered environment that plays a critical role in facilitating ion transport. Here we show that, in contrast to this prevailing view, ionic conductivity in the static, ordered environment of the crystalline phase can be greater than that in the equivalent amorphous material above Tg. Moreover, we demonstrate that ion transport in crystalline polymer electrolytes can be dominated by the cations, whereas both ions are generally mobile in the amorphous phase. Restriction of mobility to the lithium cation is advantageous for battery applications. The realization that order can promote ion transport in polymers is interesting in the context of electronically conducting polymers, where crystallinity favours electron transport.

  7. Fluorine-doped antiperovskite electrolyte for all-solid-state Lithium-ion batteries

    SciTech Connect

    Li, Yutao; Zhou, Weidong; Xin, Sen; Li, Shuai; Zhu, Jinlong; Lu, Xujie; Cui, Zhiming; Jia, Quanxi; Zhou, Jianshi; Zhao, Yusheng; Goodenough, John B.

    2016-06-30

    A fluorine-doped antiperovskite Li-ion conducto Li2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li+/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li2OHCl. As a result, an all-solid-state Li/LiFePO4 with F-dope Li2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

  8. Fluorine-doped antiperovskite electrolyte for all-solid-state Lithium-ion batteries

    DOE PAGES

    Li, Yutao; Zhou, Weidong; Xin, Sen; ...

    2016-06-30

    A fluorine-doped antiperovskite Li-ion conducto Li2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li+/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li2OHCl. As a result, an all-solid-state Li/LiFePO4 with F-dope Li2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

  9. Fluorine-Doped Antiperovskite Electrolyte for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Li, Yutao; Zhou, Weidong; Xin, Sen; Li, Shuai; Zhu, Jinlong; Lü, Xujie; Cui, Zhiming; Jia, Quanxi; Zhou, Jianshi; Zhao, Yusheng; Goodenough, John B

    2016-08-16

    A fluorine-doped antiperovskite Li-ion conductor Li2 (OH)X (X=Cl, Br) is shown to be a promising candidate for a solid electrolyte in an all-solid-state Li-ion rechargeable battery. Substitution of F(-) for OH(-) transforms orthorhombic Li2 OHCl to a room-temperature cubic phase, which shows electrochemical stability to 9 V versus Li(+) /Li and two orders of magnitude higher Li-ion conductivity than that of orthorhombic Li2 OHCl. An all-solid-state Li/LiFePO4 with F-doped Li2 OHCl as the solid electrolyte showed good cyclability and a high coulombic efficiency over 40 charge/discharge cycles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Electrolyte stability determines scaling limits for solid-state 3D Li ion batteries.

    PubMed

    Ruzmetov, Dmitry; Oleshko, Vladimir P; Haney, Paul M; Lezec, Henri J; Karki, Khim; Baloch, Kamal H; Agrawal, Amit K; Davydov, Albert V; Krylyuk, Sergiy; Liu, Yang; Huang, Jiany; Tanase, Mihaela; Cumings, John; Talin, A Alec

    2012-01-11

    Rechargeable, all-solid-state Li ion batteries (LIBs) with high specific capacity and small footprint are highly desirable to power an emerging class of miniature, autonomous microsystems that operate without a hardwire for power or communications. A variety of three-dimensional (3D) LIB architectures that maximize areal energy density has been proposed to address this need. The success of all of these designs depends on an ultrathin, conformal electrolyte layer to electrically isolate the anode and cathode while allowing Li ions to pass through. However, we find that a substantial reduction in the electrolyte thickness, into the nanometer regime, can lead to rapid self-discharge of the battery even when the electrolyte layer is conformal and pinhole free. We demonstrate this by fabricating individual, solid-state nanowire core-multishell LIBs (NWLIBs) and cycling these inside a transmission electron microscope. For nanobatteries with the thinnest electrolyte, ≈110 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. With electrolyte thickness increased to 180 nm, the self-discharge rate is reduced substantially, and the NWLIBs maintain a potential above 2 V for over 2 h. Analysis of the nanobatteries' electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes directly through the electrolyte. Our study illustrates that, at these nanoscale dimensions, the increased electric field can lead to large electronic current in the electrolyte, effectively shorting the battery. The scaling of this phenomenon provides useful guidelines for the future design of 3D LIBs.

  11. Poly(ethylene oxide)-Based Composite Electrolytes Filled with Periodic Mesoporous Silica for Solid State Ionics

    NASA Astrophysics Data System (ADS)

    Tominaga, Yoichi; Morita, Masahiro; Asai, Shigeo; Sumita, Masao

    Mesoporous silica (MPS) was used for poly(ethylene oxide) (PEO)-based solid polymer electrolytes as novel inorganic filler. For improvement in ionic conductivity in solid state, a room temperature ionic liquid (IL), 1-ethyl-3-methylimidazolium tetrafluoroborate, was introduced into periodic nano-tunnels of MPS, and the modified MPS (IL-MPS) was filled with PEO-LiBF4 electrolyte. Ionic conductivity of neat-MPS-filled composites was approximately 4-fold higher than that of the original electrolyte. On the other hand, the conductivity was more than 11-fold enhanced by addition of IL-MPS, to be more than 10-6 S/cm at 30°C and at least 10 wt% silica contents. The conductivity increased with increasing IL-MPS contents, to be a maximum value of approximately 3×10-6 S/cm at 30°C and at 40 wt%. Dynamic mechanical measurements for neat- and IL-MPS composites revealed that the addition of fillers improves storage modulus of PEO-based electrolytes at room temperature. The addition of IL-MPS was able to realize the improvement in both ionic conductivity and storage modulus.

  12. In-situ, non-destructive acoustic characterization of solid state electrolyte cells

    NASA Astrophysics Data System (ADS)

    Schmidt, Robert D.; Sakamoto, Jeffrey

    2016-08-01

    Solid-state electrolytes such as cubic Li6.25Al0.25La3Zr2O12 (LLZO) can enable solid-state batteries, metallic lithium anodes and higher voltage cathodes. However, the stability of cubic LLZO is affected by current density. In beta alumina solid electrolyte, microstructural failure was caused by Na dendrite penetration, and was shown to be a function of the fracture toughness, KIC. The relationship between dendrite penetration and KIC indicates electronic failure is related to creation of microstructural damage, and the microstructural damage may be used as an indicator of imminent electronic failure. To monitor microstructural damage during cycling, we developed a non-invasive, in-situ cell monitoring apparatus to help to correlate mechanical stability with Li-ion current density in LLZO. A pulse-echo transducer was integrated into all solid-state Li-LLZO-Li cells. The capability enables the characterization of microscopic inhomogeneities through the careful measurement of changes to the elastic moduli. The elastic moduli and fracture toughness have been previously reported for dense (>99%) specimens, but monitoring of the relative change in moduli during cycling has not been explored. In this study, an acoustic monitoring method is presented to monitor LLZO specimens during cycling.

  13. Current limit diagrams for dendrite formation in solid-state electrolytes for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Raj, R.; Wolfenstine, J.

    2017-03-01

    We build upon the concept that nucleation of lithium dendrites at the lithium anode-solid state electrolyte interface is instigated by the higher resistance of grain boundaries that raises the local electro-chemical potential of lithium, near the lithium-electrode. This excess electro-chemo-mechanical potential, however, is reduced by the mechanical back stress generated when the dendrite is formed within the electrolyte. These parameters are coalesced into an analytical model that prescribes a specific criterion for dendrite formation. The results are presented in the form of current limit diagrams that show the ;safe; and ;fail; regimes for battery function. A higher conductivity of the electrolyte can reduce dendrite formation.

  14. Superior ion-conducting hybrid solid electrolyte for all-solid-state batteries.

    PubMed

    Kim, Jae-Kwang; Scheers, Johan; Park, Tae Joo; Kim, Youngsik

    2015-02-01

    Herein, we developed a high-performance lithium ion conducting hybrid solid electrolyte, consisted of LiTFSI salt, Py14 TFSI ionic liquid, and TiO2 nanoparticles. The hybrid solid electrolyte prepared by a facile method had high room temperature ionic conductivity, excellent thermal stability and low interface resistance with good contact. In addition, the lithium transference number was highly increased by the scavenger effect of TiO2 nanoparticles. With the hybrid solid electrolyte, the pouch-type solid-state battery exhibited high initial discharge capacity of 150 mA h g(-1) at room temperature, and even at 1 C, the reversible capacity was as high as 106 mA h g(-1) .

  15. Composite solid polymer electrolyte membranes

    DOEpatents

    Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

    2006-05-30

    The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

  16. Composite solid polymer electrolyte membranes

    DOEpatents

    Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

    2001-06-19

    The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

  17. Rechargeable solid-state battery using a proton-conducting composite as electrolyte

    NASA Astrophysics Data System (ADS)

    Lakshmi, N.; Chandra, S.

    Proton-conducting composites of heteropolyacid hydrates (phospbotungstic acid, PTA and phosphomolybdic acid, PMA) with dispersoids such as insulating Al 2O 3, Al 2(SO 4) 3·16H 2O and (NH 4) 10W 12O 41·2H 2O are prepared for use as possible solid-state electrolytes in batteries. Bulk electrical conductivity as a function of composition is reported. Rechargeable solid-state proton batteries are fabricated and characterized. A cell with the configuration Zn+ZnSO 4·7H 2O+MH x|PMA+APT|PbO 2+V 2O 5+C+E gives an open circuit voltage of 1.5 V and can run for >850 h at a current drain of 2.4 μA cm -2. The cell can be recharged without much loss up to 18-20 cycles.

  18. Solid state, transparent, cadmium sulfide-polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Kothurkar, Nikhil K.

    This dissertation deals with the preparation and characterization of solid state, transparent CdS-polymer nanocomposites for potential applications in optical limiting, lenses and photovoltaics. The focus of this research was controlling CdS aggregation to obtain 1 mm thick, films with a transmittance >85%. CdS-polysulfone nanocomposites gave transparent sols using thiol-capping agents however solid films obtained, were translucent to opaque. CdS-epoxy nanocomposites gave 1 mm thick films with >85% transmittance. Oligomeric polyoxypropylene diamine stabilizers were used to shield the inter particle forces and increase the viscosity of the medium to give air stable sols. Films were obtained by curing the CdS sols with an epoxy resin system. The band edge of the nanocomposites showed a shoulder corresponding to the absorption from the CdS particles. A majority of small amorphous and non-stoichiometric (richer in Cd) particles <5 nm were observed in TEM micrographs. Relatively fewer CdS aggregates in the range of tens to hundreds of nanometers were also detected. Aggregates were generally more numerous in films as compared to sols. The two-photon absorption coefficient of the CdS particles in the films showed a 30-fold reduction compared to bulk CdS. This was attributed to the lack of crystallinity of particles. The films were stable up to 300°C. CdS aggregation in the CdS-epoxy system depends on a number of factors including temperature, stabilizer concentration, stabilizer molar mass and US concentration. Effective aggregation control yields transparent films. Factors affecting the band edge and transparency of the films were detected and regression models were fitted to the data. Temperature, stabilizer concentration and CdS concentration had significant effects on the band edge and transparency. Interactions between temperature-stabilizer concentration and temperature-CdS concentration had significant effects on the band edge. Band edge tunability with

  19. Co-existence of LiI and KI in filler-free, quasi-solid-state electrolyte for efficient and stable dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Agarwala, S.; Thummalakunta, L. N. S. A.; Cook, C. A.; Peh, C. K. N.; Wong, A. S. W.; Ke, L.; Ho, G. W.

    A quasi-solid-state electrolyte employing a poly (ethylene oxide)/LiI system without a filler is evaluated. The electrolyte is optimized for various potassium iodide (KI) concentrations. The electrolyte containing 14.5 wt.% KI exhibits the highest conductivity (3.0 × 10 -3 S cm -1). An efficiency of 4.5% is achieved using this composition of the electrolyte. It is shown that the introduction of KI in a conventional PEO/I 2/LiI electrolyte system prevents the crystallization of the polymer matrix and enhances the ionic conductivity. The energy conversion efficiency of the device is further enhanced to 5.8% by incorporating a light-scattering layer.

  20. Ionic correlations and failure of Nernst-Einstein relation in solid-state electrolytes

    NASA Astrophysics Data System (ADS)

    Marcolongo, Aris; Marzari, Nicola

    2017-07-01

    A microscopic understanding of fast ionic transport is fundamental to design novel solid-state electrolytes. We address the role of correlations in these systems and study in detail the tracer and charge diffusion coefficients, deriving a novel inequality between these two quantities. We investigate the failure of the Nernst-Einstein and the physical consequences of a nontrivial Haven ratio with extensive first-principles molecular dynamics in the fast ion conductor Li10GeP2S12 . Last, we show that the approximate tracer diffusion still provides accurate activation free energies.

  1. Raising the conductivity of crystalline polymer electrolytes by aliovalent doping.

    PubMed

    Zhang, Chuhong; Staunton, Edward; Andreev, Yuri G; Bruce, Peter G

    2005-12-28

    Polymer electrolytes, salts dissolved in solid polymers, hold the key to realizing all solid-state devices such as rechargeable lithium batteries, electrochromic displays, or SMART windows. For 25 years conductivity was believed to be confined to amorphous polymer electrolytes, all crystalline polymer electrolytes were thought to be insulators. However, recent results have demonstrated conductivity in crystalline polymer electrolytes, although the levels at room temperature are too low for application. Here we show, for the first time, that it is possible to raise significantly the level of ionic conductivity by aliovalent doping. The conductivity may be raised by 1.5 orders of magnitude if the SbF6- ion in the crystalline conductor poly(ethylene oxide)6:LiSbF6 is replaced by less than 5 mol % SiF6(2-), thus introducing additional, mobile, Li+ ions into the structure to maintain electroneutrality.

  2. Rechargeable solid polymer electrolyte battery cell

    DOEpatents

    Skotheim, Terji

    1985-01-01

    A rechargeable battery cell comprising first and second electrodes sandwiching a solid polymer electrolyte comprising a layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte adjacent said polymer blend and a layer of dry solid polymer electrolyte adjacent said layer of polymer blend and said second electrode.

  3. Communication: Conductivity enhancement in plastic-crystalline solid-state electrolytes.

    PubMed

    Geirhos, K; Lunkenheimer, P; Michl, M; Reuter, D; Loidl, A

    2015-08-28

    Finding new ionic conductors that enable significant advancements in the development of energy-storage devices is a challenging goal of current material science. Aside of material classes as ionic liquids or amorphous ion conductors, the so-called plastic crystals (PCs) have been shown to be good candidates combining high conductivity and favorable mechanical properties. PCs are formed by molecules whose orientational degrees of freedom still fluctuate despite the material exhibits a well-defined crystalline lattice. In the present work, we show that the conductivity of Li(+) ions in succinonitrile, the most prominent molecular PC electrolyte, can be enhanced by several decades when replacing part of the molecules in the crystalline lattice by larger ones. Dielectric spectroscopy reveals that this is accompanied by a stronger coupling of ionic and reorientational motions. These findings, which can be understood in terms of an optimized "revolving door" mechanism, open a new path towards the development of better solid-state electrolytes.

  4. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, M.; Abraham, K.M.

    1993-10-12

    This invention pertains to Lithium batteries using Li ion (Li[sup +]) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride). 3 figures.

  5. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, Mohamed; Abraham, Kuzhikalail M.

    1993-01-01

    This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

  6. Semiconductor/Solid Electrolyte Junctions for Optical Information Storage. Electrochromic Effects on Heptylviologen Incorporated within a Solid Polymer Electrolyte Cell.

    DTIC Science & Technology

    1986-05-15

    cathode5 . Electrochromic devices based upon these electrochemically reversible viologen redox couples would greatly benefit by their incorporation...electrolyte analogs. Here we wish to discuss some recent work from our laboratory on solid- state electrochromic cells in which heptyl viologen (HV2+) was...OPTICAL INFORMATION STORAGE. ELECTROCHROMIC EFFECTS QN HEPTYLVIOLOGEN INCORPORATED WITHIN A SOLID POLYMER ELECTROLYTE CELL By Anthony F. Sammells and

  7. Microwave Crystallization of Lithium Aluminum Germanium Phosphate Solid-State Electrolyte.

    PubMed

    Mahmoud, Morsi M; Cui, Yuantao; Rohde, Magnus; Ziebert, Carlos; Link, Guido; Seifert, Hans Juergen

    2016-06-23

    Lithium aluminum germanium phosphate (LAGP) glass-ceramics are considered as promising solid-state electrolytes for Li-ion batteries. LAGP glass was prepared via the regular conventional melt-quenching method. Thermal, chemical analyses and X-ray diffraction (XRD) were performed to characterize the prepared glass. The crystallization of the prepared LAGP glass was done using conventional heating and high frequency microwave (MW) processing. Thirty GHz microwave (MW) processing setup were used to convert the prepared LAGP glass into glass-ceramics and compared with the conventionally crystallized LAGP glass-ceramics that were heat-treated in an electric conventional furnace. The ionic conductivities of the LAGP samples obtained from the two different routes were measured using impedance spectroscopy. These samples were also characterized using XRD and scanning electron microscopy (SEM). Microwave processing was successfully used to crystallize LAGP glass into glass-ceramic without the aid of susceptors. The MW treated sample showed higher total, grains and grain boundary ionic conductivities values, lower activation energy and relatively larger-grained microstructure with less porosity compared to the corresponding conventionally treated sample at the same optimized heat-treatment conditions. The enhanced total, grains and grain boundary ionic conductivities values along with the reduced activation energy that were observed in the MW treated sample was considered as an experimental evidence for the existence of the microwave effect in LAGP crystallization process. MW processing is a promising candidate technology for the production of solid-state electrolytes for Li-ion battery.

  8. Transition from Superlithiophobicity to Superlithiophilicity of Garnet Solid-State Electrolyte.

    PubMed

    Luo, Wei; Gong, Yunhui; Zhu, Yizhou; Fu, Kun Kelvin; Dai, Jiaqi; Lacey, Steven D; Wang, Chengwei; Liu, Boyang; Han, Xiaogang; Mo, Yifei; Wachsman, Eric D; Hu, Liangbing

    2016-09-21

    All-solid-state Li-batteries using solid-state electrolytes (SSEs) offer enhanced safety over conventional Li-ion batteries with organic liquid electrolytes due to the nonflammable nature of SSEs. The superior mechanical strength of SSEs can also protect against Li dendrite penetration, which enables the use of the highest specific capacity (3861 mAh/g) and lowest redox potential (-3.04 V vs standard hydrogen electrode) anode: Li metal. However, contact between the Li metal and SSEs presents a major challenge, where a large polarization occurs at the Li metal/SSE interface. Here, the chemical properties of a promising oxide-based SSE (garnet) changed from "super-lithiophobicity" to "super-lithiophilicity" through an ultrathin coating of amorphous Si deposited by plasma-enhanced chemical vapor deposition (PECVD). The wettability transition is due to the reaction between Li and Si and the in situ formation of lithiated Si. As a result, symmetric cells composed of a Si-coated garnet-structured SSE and Li metal electrodes exhibited much smaller impedance and excellent stability upon plating/stripping cycles compared to cells using bare garnet SSE. Specifically, the interfacial resistance between Li and garnet dramatically decreased from 925 to 127 Ω cm(2) when lithiated Si was formed on the garnet. Our discovery of switchable lithiophobic-lithiophilic surfaces to improve the Li metal/SSE interface opens opportunities for improving many other SSEs.

  9. All solid state lithium batteries based on lamellar garnet-type ceramic electrolytes

    NASA Astrophysics Data System (ADS)

    Du, Fuming; Zhao, Ning; Li, Yiqiu; Chen, Cheng; Liu, Ziwei; Guo, Xiangxin

    2015-12-01

    All solid-state lithium batteries are constructed by using highly conducting Ta-doped Li7La3Zr2O12 (LLZTO) as the solid electrolytes as well as the supports, coated with composite cathodes consisting of poly(vinylidene fluoride) (PVdF):LiTFSI, Ketjen Black, and carbon-coated LiFePO4 on one side and attached with Li anode on the other side. At 60 °C, the batteries show the first discharge capacity of 150 mAh g-1 at 0.05 C and 93% capacity retention after 100 cycles. As the current density increases from 0.05 C to 1 C, the specific capacity decreases from 150 mAh g-1 to 100 mAh g-1. Further elevated temperature up to 100 °C leads to further improved performance, i.e. 126 mAh g-1 at 1 C and 99% capacity retention after 100 cycles. This good performance can be attributed to the highly conducting ceramic electrolytes, the optimum electronic and ionic conducting networks in the composite cathodes, and closely contacted cathode/LLZTO interface. These results indicate that the present strategy is promising for development of high-performance solid-state Li-ion batteries operated at medium temperature.

  10. Nanostructured Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Odusanya, Omolola; Singh, Mohit; Balsara, Nitash

    2006-03-01

    We present results on work on polystyrene-b-polyethyleneoxide copolymer electrolyte membranes. The volume fraction of the ethylene oxide block is 0.38 and molecular weight of each block is 36 kg/mol and 25 kg/mol respectively for the polystyrene and ethyleneoxide blocks. These electrolytes were made by doping with lithium bis(trifluoromethylsulfonyl)imide salt with the ratio of Li ion / ethylene oxide units ranging from 0.02 to 0.1. The salt/polymer samples were pressed into 1.0mm thick and 4.0 mm ID pellets in an air-free environment and measurements were made from 80^oC to 120^oC. Transmission Electron Microscopy and Small Angle X-ray Scattering experiment results indicate that our samples have a perforated hexagonal morphology. Conductivity results using AC impedance spectroscopy show that we are able to achieve values of ˜ 0.0001 S/cm, well within the theoretical upper limit expected for these samples while maintaining a high mechanical integrity of about 0.1GPa as determined from rheology. Achieving the combination of high conductivity with mechanical strength, which we observe in our results, has been a major problem in the battery research community.

  11. Ionic conductor with high conductivity as single-component electrolyte for efficient solid-state dye-sensitized solar cells.

    PubMed

    Wang, Hong; Li, Juan; Gong, Feng; Zhou, Gang; Wang, Zhong-Sheng

    2013-08-28

    Imidazolium iodide is an often used component in iodine-based dye-sensitized solar cells (DSSCs), but it cannot operate an efficient DSSC in the absence of iodine due to its low conductivity. For this study, lamellar solid iodide salts of imidazolium or piperidinium with an N-substituted propargyl group have been prepared and applied in solid-state DSSCs. Owing to the high conductivity arising from the lamellar structure, these solid-state ionic conductors can be used as single-component solid electrolytes to operate solid-state DSSCs efficiently without any additives in the electrolyte and post-treatments on the dye-loaded TiO2 films. With a propargyl group attached to the imidazolium ring, the conductivity is enhanced by about 4 × 10(4)-fold as compared to the alkyl-substituted imidazolium iodide. Solid-state DSSC with the 1-propargyl-3-methylimidazolium iodide as the single-component solid-state electrolyte has achieved a light-to-electricity power conversion efficiency of 6.3% under illumination of simulated AM1.5G solar light (100 mW cm(-2)), which also exhibits good long-term stability under continuous 1 sun soaking for 1500 h. This finding paves the way for development of high-conductivity single-component solid electrolytes for use in efficient solid-state DSSCs.

  12. High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

    PubMed

    Akhtar, M Shaheer; Kwon, Soonji; Stadler, Florian J; Yang, O Bong

    2013-06-21

    Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.

  13. Toward electrochromic device using solid electrolyte with polar polymer host.

    PubMed

    Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

    2009-06-11

    Polymer electrolyte is an important component in many multilayer devices such as batteries, fuel cells, and electrochromic devices. The effects of polymer electrolyte solidification on the ionic movement and device performance are presented based on near-infrared (IR) (860-2500 nm) electrochromic (EC) devices using the conducting polymer polyaniline. EC devices using electrolyte with polar polymer host of P(VDF-TrFE) show stable and reversible light modulation up to 65% in gel state and 30% in solid state. This is significantly improved when compared to devices with solidified nonpolar polymer host which retains less than 10% light modulation. Electrochemical impedance combined with in situ light modulation measurement identifies various key characteristics exerted by the electrolyte states on device performance. Gel-state devices are affected by the amount of dissociated ions while ionic movement in the electrolyte bulk and through the electrolyte/EC material interface dictates the light modulation in semisolid devices. For solid-state devices, electronic leakage, ionic dissociation, and interaction with electrochrome molecules have been found to limit the operation.

  14. Conformal, Nanoscale ZnO Surface Modification of Garnet-Based Solid-State Electrolyte for Lithium Metal Anodes.

    PubMed

    Wang, Chengwei; Gong, Yunhui; Liu, Boyang; Fu, Kun; Yao, Yonggang; Hitz, Emily; Li, Yiju; Dai, Jiaqi; Xu, Shaomao; Luo, Wei; Wachsman, Eric D; Hu, Liangbing

    2017-01-11

    Solid-state electrolytes are known for nonflammability, dendrite blocking, and stability over large potential windows. Garnet-based solid-state electrolytes have attracted much attention for their high ionic conductivities and stability with lithium metal anodes. However, high-interface resistance with lithium anodes hinders their application to lithium metal batteries. Here, we demonstrate an ultrathin, conformal ZnO surface coating by atomic layer deposition for improved wettability of garnet solid-state electrolytes to molten lithium that significantly decreases the interface resistance to as low as ∼20 Ω·cm(2). The ZnO coating demonstrates a high reactivity with lithium metal, which is systematically characterized. As a proof-of-concept, we successfully infiltrated lithium metal into porous garnet electrolyte, which can potentially serve as a self-supported lithium metal composite anode having both high ionic and electrical conductivity for solid-state lithium metal batteries. The facile surface treatment method offers a simple strategy to solve the interface problem in solid-state lithium metal batteries with garnet solid electrolytes.

  15. High-temperature solid-state dye-sensitized solar cells based on organic ionic plastic crystal electrolytes.

    PubMed

    Li, Qing; Zhao, Jie; Sun, Baoquan; Lin, Bencai; Qiu, Lihua; Zhang, Yueguang; Chen, Xiaojian; Lu, Jianmei; Yan, Feng

    2012-02-14

    Organic ionic plastic crystal, 1-ethyl-1-methyl pyrrolidinium iodide (P(12) I), is employed as the solid-state electrolytes for dye-sensitized solar cells. The fabricated solid-state devices show an overall power conversion efficiency of ~5.8% under AM 1.5 radiation (50 mW/cm(2) ) and excellent long-term stability at 80 °C.

  16. First-principles material modeling of solid-state electrolytes with the spinel structure.

    PubMed

    Mees, Maarten J; Pourtois, Geoffrey; Rosciano, Fabio; Put, Brecht; Vereecken, Philippe M; Stesmans, André

    2014-03-21

    Ionic diffusion through the novel (AlxMg1-2xLix)Al2O4 spinel electrolyte is investigated using first-principles calculations, combined with the Kinetic Monte Carlo algorithm. We observe that the ionic diffusion increases with the lithium content x. Furthermore, the structural parameters, formation enthalpies and electronic structures of (AlxMg1-2xLix)Al2O4 are calculated for various stoichiometries. The overall results indicate the (AlxMg1-2xLix)Al2O4 stoichiometries x = 0.2…0.3 as most promising. The (AlxMg1-2xLix)Al2O4 electrolyte is a potential candidate for the all-spinel solid-state battery stack, with the material epitaxially grown between well-known spinel electrodes, such as LiyMn2O4 and Li4+3yTi5O12 (y = 0…1). Due to their identical crystal structure, a good electrolyte-electrode interface is expected.

  17. An all-solid-state lithium-sulfur battery using two solid electrolytes having different functions

    NASA Astrophysics Data System (ADS)

    Nagata, Hiroshi; Chikusa, Yasuo

    2016-10-01

    All-solid-state lithium-sulfur batteries are expected to be valuable next generation batteries. To improve the performance of all-solid-state lithium-sulfur batteries, it is essential to raise both the reactivity of sulfur and the ionic conductivity of the positive composite electrode. For achieving this, we investigate a positive composite electrode prepared using P2S5 and a solid electrolyte with a high ionic conductivity. As a result, we have found that the lithium-sulfur cell exhibits a relatively low activation energy together with high ionic conductivity. The positive composite electrode exhibits an extremely high capacity of 1550 mA h g-1 (sulfur) at 1.3 mA cm-2 and 25 °C. Moreover, when using the positive electrode, the energy densities at the cell level (18650) are 540 W h kg-1 and 990 W h L-1, estimated from the equivalent structure of a current lithium-ion battery.

  18. Method of producing ceramic distribution members for solid state electrolyte cells

    NASA Technical Reports Server (NTRS)

    Clark, Douglas J. (Inventor); Galica, Leo M. (Inventor); Losey, Robert W. (Inventor); Suitor, Jerry W. (Inventor)

    1995-01-01

    A solid state electrolyte cells apparatus and method of producing is disclosed. The apparatus can be used for separating oxygen from an oxygen-containing feedstock or as a fuel cell for reacting fluids. Cells can be stacked so that fluids can be introduced and removed from the apparatus through ceramic distribution members having ports designed for distributing the fluids in parallel flow to and from each cell. The distribution members can also serve as electrodes to membranes or as membrane members between electrodes, The distribution member design does not contain any horizontal internal ports which allows the member to be thin. A method of tape casting in combination with an embossing method allows intricate radial ribs and bosses to be formed on each distribution member. The bosses serve as seals for the ports and allow the distribution members to be made without any horizontal internal ports.

  19. Ceramic distribution members for solid state electrolyte cells and method of producing

    NASA Technical Reports Server (NTRS)

    Clark, Douglas J. (Inventor); Galica, Leo M. (Inventor); Losey, Robert W. (Inventor); Suitor, Jerry W. (Inventor)

    1993-01-01

    A solid state electrolyte cells apparatus and method of producing is disclosed. The apparatus can be used for separating oxygen from an oxygen-containing feedstock or as a fuel cell for reacting fluids. Cells can be stacked so that fluids can be introduced and removed from the apparatus through ceramic distribution members having ports designed for distributing the fluids in parallel flow to and from each cell. The distribution members can also serve as electrodes to membranes or as membrane members between electrodes. The distribution member design does not contain any horizontal internal ports which allows the member to be thin. A method of tape casting in combination with an embossing method allows intricate radial ribs and bosses to be formed on each distribution member. The bosses serve as seals for the ports and allow the distribution members to be made without any horizontal internal ports.

  20. Table 2.4. Cell voltages with solid state electrolyte systems

    NASA Astrophysics Data System (ADS)

    Holze, R.

    This document is part of Volume 9 `Electrochemistry', Subvolume A, of Landolt-Börnstein - Group IV `Physical Chemistry'. The document lists normal voltages of cells with solid state electrolyte systems. The cells are composed of the following materials: silver (Ag), aluminium (Al), barium (Ba), bismuth (Bi), carbon (C), cadmium (Cd), cobalt (Co), chromium (Cr), cesium (Cs), copper (Cu), iron (Fe), germanium (Ge), hafnium (Hf), iridium (Ir), potassium (K), lanthanum (La), lithium (Li), magnesium (Mg), manganese (Mn), molybdenum (Mo), nitrogen (N), natrium (Na), niobium (Nb), neodymium (Nd), nickel (Ni), lead (Pb), palladium (Pd), rhodium (Rh), ruthenium (Ru), antimony (Sb), samarium (Sm), tin (Sn), strontium (Sr), tantalum (Ta), tellurium (Te), thorium (Th), thallium (Tl), uranium (U), yttrium (Y), zinc (Zn), zirconium (Zr). The compositions of the cells are given along with, where available, the temperatures of mesurements of the voltages.

  1. Polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Gottesfeld, S.

    The recent increase in attention to polymer electrolyte fuel cells (PEFC's) is the result of significant technical advances in this technology and the initiation of some projects for the demonstration of complete PEFC-based power system in a bus or in a passenger car. A PEFC powered vehicle has the potential for zero emission, high energy conversion efficiency and extended range compared to present day battery powered EV's. This paper describes recent achievements in R&D on PEFC's. The major thrust areas have been: (1) demonstration of membrane/electrode assemblies with stable high performance in life tests lasting 4000 hours, employing ultra-low Pt loadings corresponding to only 1/2 oz of Pt for the complete power source of a passenger car; (2) effective remedies for the high sensitivity of the Pt electrocatalyst to impurities in the fuel feed stream; and (3) comprehensive evaluation of the physicochemical properties of membrane and electrodes in the PEFC, clarifying the water management issues and enabling effective codes and diagnostics for this fuel cell.

  2. Microwave Crystallization of Lithium Aluminum Germanium Phosphate Solid-State Electrolyte

    PubMed Central

    Mahmoud, Morsi M.; Cui, Yuantao; Rohde, Magnus; Ziebert, Carlos; Link, Guido; Seifert, Hans Juergen

    2016-01-01

    Lithium aluminum germanium phosphate (LAGP) glass-ceramics are considered as promising solid-state electrolytes for Li-ion batteries. LAGP glass was prepared via the regular conventional melt-quenching method. Thermal, chemical analyses and X-ray diffraction (XRD) were performed to characterize the prepared glass. The crystallization of the prepared LAGP glass was done using conventional heating and high frequency microwave (MW) processing. Thirty GHz microwave (MW) processing setup were used to convert the prepared LAGP glass into glass-ceramics and compared with the conventionally crystallized LAGP glass-ceramics that were heat-treated in an electric conventional furnace. The ionic conductivities of the LAGP samples obtained from the two different routes were measured using impedance spectroscopy. These samples were also characterized using XRD and scanning electron microscopy (SEM). Microwave processing was successfully used to crystallize LAGP glass into glass-ceramic without the aid of susceptors. The MW treated sample showed higher total, grains and grain boundary ionic conductivities values, lower activation energy and relatively larger-grained microstructure with less porosity compared to the corresponding conventionally treated sample at the same optimized heat-treatment conditions. The enhanced total, grains and grain boundary ionic conductivities values along with the reduced activation energy that were observed in the MW treated sample was considered as an experimental evidence for the existence of the microwave effect in LAGP crystallization process. MW processing is a promising candidate technology for the production of solid-state electrolytes for Li-ion battery. PMID:28773627

  3. Bubble Growth and Dynamics in a Strongly Superheated Electrolyte within a Solid-State Nanopore

    NASA Astrophysics Data System (ADS)

    Levine, Edlyn; Nagashima, Gaku; Burns, Michael; Golovchenko, Jene

    2015-03-01

    Extreme localized superheating and homogeneous vapor bubble nucleation have recently been demonstrated in a single nanopore in thin, solid state membranes. Aqueous electrolytic solution within the pore is superheated to well above its boiling point by Joule heating from ionic current driven through the pore. Continued heating of the metastable liquid leads to nucleation of a vapor bubble in the pore followed by explosive growth. Here we report on the growth dynamics of the vapor bubble after nucleation in the strongly superheated liquid. The process is modeled by numerically solving the Rayleigh-Plesset equation coupled with energy conservation and a Stefan boundary condition. The initial temperature distribution, peaked at the pore center, is taken to be radially symmetric. Energy conservation includes a Joule heating source term dependent on the bubble radius, which grows to constrict ionic current through the nanopore. Temperature-dependent properties of the electrolyte and the vapor are incorporated in the calculation. Comparison of the model to experimental results shows an initial bubble growth velocity of 50m/s and total bubble lifetime of 16ns. This work was supported by NIH Grant #5R01HG003703 to J.A. Golovchenko.

  4. High elastic modulus polymer electrolytes

    DOEpatents

    Balsara, Nitash Pervez; Singh, Mohit; Eitouni, Hany Basam; Gomez, Enrique Daniel

    2013-10-22

    A polymer that combines high ionic conductivity with the structural properties required for Li electrode stability is useful as a solid phase electrolyte for high energy density, high cycle life batteries that do not suffer from failures due to side reactions and dendrite growth on the Li electrodes, and other potential applications. The polymer electrolyte includes a linear block copolymer having a conductive linear polymer block with a molecular weight of at least 5000 Daltons, a structural linear polymer block with an elastic modulus in excess of 1.times.10.sup.7 Pa and an ionic conductivity of at least 1.times.10.sup.-5 Scm.sup.-1. The electrolyte is made under dry conditions to achieve the noted characteristics.

  5. Development of Bipolar All-solid-state Lithium Battery Based on Quasi-solid-state Electrolyte Containing Tetraglyme-LiTFSA Equimolar Complex

    PubMed Central

    Gambe, Yoshiyuki; Sun, Yan; Honma, Itaru

    2015-01-01

    The development of high energy–density lithium-ion secondary batteries as storage batteries in vehicles is attracting increasing attention. In this study, high-voltage bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex were prepared, and the performance of the device was evaluated. Via the successful production of double-layered and triple-layered high-voltage devices, it was confirmed that these stacked batteries operated properly without any internal short-circuits of a single cell within the package: Their plateau potentials (6.7 and 10.0 V, respectively) were two and three times that (3.4 V) of the single-layered device, respectively. Further, the double-layered device showed a capacity retention of 99% on the 200th cycle at 0.5 C, which is an indication of good cycling properties. These results suggest that bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex could readily produce a high voltage of 10 V. PMID:25746860

  6. Development of bipolar all-solid-state lithium battery based on quasi-solid-state electrolyte containing tetraglyme-LiTFSA equimolar complex.

    PubMed

    Gambe, Yoshiyuki; Sun, Yan; Honma, Itaru

    2015-03-09

    The development of high energy-density lithium-ion secondary batteries as storage batteries in vehicles is attracting increasing attention. In this study, high-voltage bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex were prepared, and the performance of the device was evaluated. Via the successful production of double-layered and triple-layered high-voltage devices, it was confirmed that these stacked batteries operated properly without any internal short-circuits of a single cell within the package: Their plateau potentials (6.7 and 10.0 V, respectively) were two and three times that (3.4 V) of the single-layered device, respectively. Further, the double-layered device showed a capacity retention of 99% on the 200th cycle at 0.5 C, which is an indication of good cycling properties. These results suggest that bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex could readily produce a high voltage of 10 V.

  7. Silica nanoparticle doped organic ionic plastic crystal electrolytes for highly efficient solid-state dye-sensitized solar cells.

    PubMed

    Shi, Chengzhen; Qiu, Lihua; Chen, Xiaojian; Zhang, Haigang; Wang, Lei; Yan, Feng

    2013-02-01

    Organic ionic plastic crystal, 1-propyl-1-methylpyrrolidinium iodide (P₁₃I), which possesses a broad plastic phase from -36 to 135 °C, was doped with silica nanoparticles (SiO₂ NPs) and 1-ethyl-3-methylimidazolium iodide (EMII), for the preparation of SiO₂/EMII/P₁₃I solid-state electrolytes for dye-sensitized solar cells (DSSCs). The thermal properties of all the electrolytes, including solid-solid phase transitions and melting temperatures, were investigated by differential scanning calorimetry (DSC). The effect of silica particles on the ionic conductivity, diffusion of I⁻/I₃⁻ redox couple in electrolytes, and photovoltaic performance for solid-state DSSCs were investigated. The fabricated solid-state DSSCs yielded a high power conversion efficiency of 5.25% under simulated air mass 1.5 solar spectrum illuminations at 50 mW cm⁻². Furthermore, the DSSCs based on SiO₂/EMII/P₁₃I solid-state electrolytes show good stability after an accelerating aging test, demonstrating potential practical applications.

  8. Water-resistant, solid-state, dye-sensitized solar cells based on hydrophobic organic ionic plastic crystal electrolytes.

    PubMed

    Li, Shichao; Qiu, Lihua; Shi, Chengzhen; Chen, Xiaojian; Yan, Feng

    2014-02-26

    Water-resistant, solid-state, dye-sensitized solar cells with excellent long-term stability at 100% relative humidity and at 50 °C are fabricated on the basis of a novel hydrophobic organic ionic plastic crystal electrolyte and hybrid redox couple. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Scattering-layer-induced energy storage function in polymer-based quasi-solid-state dye-sensitized solar cells

    PubMed Central

    Zhang, Xi; Jiang, Hongrui

    2015-01-01

    Photo-self-charging cells (PSCs) are compact devices with dual functions of photoelectric conversion and energy storage. By introducing a scattering layer in polymer-based quasi-solid-state dye-sensitized solar cells, two-electrode PSCs with highly compact structure were obtained. The charge storage function stems from the formed ion channel network in the scattering layer/polymer electrolyte system. Both the photoelectric conversion and the energy storage functions are integrated in only the photoelectrode of such PSCs. This design of PSC could continuously output power as a solar cell with considerable efficiency after being photo-charged. Such PSCs could be applied in highly-compact mini power devices. PMID:25829547

  10. Scattering-layer-induced energy storage function in polymer-based quasi-solid-state dye-sensitized solar cells.

    PubMed

    Zhang, Xi; Jiang, Hongrui

    2015-03-09

    Photo-self-charging cells (PSCs) are compact devices with dual functions of photoelectric conversion and energy storage. By introducing a scattering layer in polymer-based quasi-solid-state dye-sensitized solar cells, two-electrode PSCs with highly compact structure were obtained. The charge storage function stems from the formed ion channel network in the scattering layer/polymer electrolyte system. Both the photoelectric conversion and the energy storage functions are integrated in only the photoelectrode of such PSCs. This design of PSC could continuously output power as a solar cell with considerable efficiency after being photo-charged. Such PSCs could be applied in highly-compact mini power devices.

  11. Anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Kim, Dae Sik; Lee, Kwan-Soo

    2013-07-23

    Solid anion exchange polymer electrolytes and compositions comprising chemical compounds comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure: ##STR00001## wherein: i) A is a spacer having the structure O, S, SO.sub.2, --NH--, --N(CH.sub.2).sub.n, wherein n=1-10, --(CH.sub.2).sub.n--CH.sub.3--, wherein n=1-10, SO.sub.2-Ph, CO-Ph, ##STR00002## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each are independently --H, --NH.sub.2, F, Cl, Br, CN, or a C.sub.1-C.sub.6 alkyl group, or any combination of thereof; ii) R.sub.9, R.sub.10, R.sub.11, R.sub.12, or R.sub.13 each independently are --H, --CH.sub.3, --NH.sub.2, --NO, --CH.sub.nCH.sub.3 where n=1-6, HC.dbd.O--, NH.sub.2C.dbd.O--, --CH.sub.nCOOH where n=1-6, --(CH.sub.2).sub.n--C(NH.sub.2)--COOH where n=1-6, --CH--(COOH)--CH.sub.2--COOH, --CH.sub.2--CH(O--CH.sub.2CH.sub.3).sub.2, --(C.dbd.S)--NH.sub.2, --(C.dbd.NH)--N--(CH.sub.2).sub.nCH.sub.3, where n=0-6, --NH--(C.dbd.S)--SH, --CH.sub.2--(C.dbd.O)--O--C(CH.sub.3).sub.3, --O--(CH.sub.2).sub.n--CH--(NH.sub.2)--COOH, where n=1-6, --(CH.sub.2).sub.n--CH.dbd.CH wherein n=1-6, --(CH.sub.2).sub.n--CH--CN wherein n=1-6, an aromatic group such as a phenyl, benzyl, phenoxy, methylbenzyl, nitrogen-substituted benzyl or phenyl groups, a halide, or halide-substituted methyl groups; and iii) wherein the composition is suitable for use in a membrane electrode assembly.

  12. A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life

    SciTech Connect

    Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; Shi, Jinan; Chu, Yong S.; Yu, Xiqian; Xu, Kaiqi; Ge, Mingyuan; Yan, Hanfei; Li, Wenjun; Gu, Lin; Hu, Yong -Sheng; Li, Hong; Chen, Liquan; Huang, Xuejie

    2016-10-31

    Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na+ ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm–1 at 25°C and 14 ms cm–1 at 80°C.

  13. A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life

    DOE PAGES

    Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; ...

    2016-10-31

    Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na+ ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm–1 at 25°C and 14 ms cm–1 at 80°C.

  14. Lithium phosphorus oxynitride solid-state thin-film electrolyte deposited and modified by bias sputtering and low temperature annealing

    SciTech Connect

    Chiu, K.-F.; Chen, C. C.; Lin, K. M.; Lo, C. C.; Lin, H. C.; Ho, W.-H.; Jiang, C. S.

    2010-07-15

    Amorphous lithium phosphorus oxynitride (LiPON) solid-state thin-film electrolyte has been deposited and characterized. The thin films were prepared by rf magnetron sputtering under various substrate biases. By fabricating under different substrate biases and applying low temperature annealing (473 K), the properties of the LiPON thin-film electrolytes and the electrolyte/cathode interfaces were modified. The ionic conductivity as high as 9.4x10{sup -4} S m{sup -1} can be obtained by depositing at optimal bias. The performances of the consequently fabricated SnO{sub 2}/LiPON/LiMn{sub 2}O{sub 4} all-solid-state lithium ion thin-film batteries were improved using the bias sputtering technique, due to the enhanced the ionic conductivity and uniform interface.

  15. Ionic conductivity enhancement of polymer electrolytes with ceramic nanowire fillers.

    PubMed

    Liu, Wei; Liu, Nian; Sun, Jie; Hsu, Po-Chun; Li, Yuzhang; Lee, Hyun-Wook; Cui, Yi

    2015-04-08

    Solid-state electrolytes provide substantial improvements to safety and electrochemical stability in lithium-ion batteries when compared with conventional liquid electrolytes, which makes them a promising alternative technology for next-generation high-energy batteries. Currently, the low mobility of lithium ions in solid electrolytes limits their practical application. The ongoing research over the past few decades on dispersing of ceramic nanoparticles into polymer matrix has been proved effective to enhance ionic conductivity although it is challenging to form the efficiency networks of ionic conduction with nanoparticles. In this work, we first report that ceramic nanowire fillers can facilitate formation of such ionic conduction networks in polymer-based solid electrolyte to enhance its ionic conductivity by three orders of magnitude. Polyacrylonitrile-LiClO4 incorporated with 15 wt % Li0.33La0.557TiO3 nanowire composite electrolyte exhibits an unprecedented ionic conductivity of 2.4 × 10(-4) S cm(-1) at room temperature, which is attributed to the fast ion transport on the surfaces of ceramic nanowires acting as conductive network in the polymer matrix. In addition, the ceramic-nanowire filled composite polymer electrolyte shows an enlarged electrochemical stability window in comparison to the one without fillers. The discovery in the present work paves the way for the design of solid ion electrolytes with superior performance.

  16. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    NASA Astrophysics Data System (ADS)

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-11-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1-xCaxAlO3-δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400-500 °C. The response current value at -300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles.

  17. A highly stable sodium solid-state electrolyte based on a dodeca/deca-borate equimolar mixture.

    PubMed

    Duchêne, L; Kühnel, R-S; Rentsch, D; Remhof, A; Hagemann, H; Battaglia, C

    2017-04-11

    Na2(B12H12)0.5(B10H10)0.5, a new solid-state sodium electrolyte is shown to offer high Na(+) conductivity of 0.9 mS cm(-1) at 20 °C, excellent thermal stability up to 300 °C, and a large electrochemical stability window of 3 V including stability towards sodium metal anodes, all essential prerequisites for a stable room-temperature 3 V all-solid-state sodium-ion battery.

  18. Polymer Electrolytes for Lithium/Sulfur Batteries

    PubMed Central

    Zhao, Yan; Zhang, Yongguang; Gosselink, Denise; Doan, The Nam Long; Sadhu, Mikhail; Cheang, Ho-Jae; Chen, Pu

    2012-01-01

    This review evaluates the characteristics and advantages of employing polymer electrolytes in lithium/sulfur (Li/S) batteries. The main highlights of this study constitute detailed information on the advanced developments for solid polymer electrolytes and gel polymer electrolytes, used in the lithium/sulfur battery. This includes an in-depth analysis conducted on the preparation and electrochemical characteristics of the Li/S batteries based on these polymer electrolytes. PMID:24958296

  19. Toward garnet electrolyte-based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface.

    PubMed

    Fu, Kun Kelvin; Gong, Yunhui; Liu, Boyang; Zhu, Yizhou; Xu, Shaomao; Yao, Yonggang; Luo, Wei; Wang, Chengwei; Lacey, Steven D; Dai, Jiaqi; Chen, Yanan; Mo, Yifei; Wachsman, Eric; Hu, Liangbing

    2017-04-01

    Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet-type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10(-3) to 10(-4) S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm(2) for the pristine garnet/Li and 75 ohm·cm(2) for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.

  20. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    PubMed

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

    2016-03-14

    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

  1. All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes.

    PubMed

    Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

    2012-02-17

    All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

  2. Realisation of an all solid state lithium battery using solid high temperature plastic crystal electrolytes exhibiting liquid like conductivity.

    PubMed

    Shekibi, Youssof; Rüther, Thomas; Huang, Junhua; Hollenkamp, Anthony F

    2012-04-07

    Replacement of volatile and combustible electrolytes in conventional lithium batteries is desirable for two reasons: safety concerns and increase in specific energy. In this work we consider the use of an ionic organic plastic crystal material (IOPC), N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF(4)], as a solid-state electrolyte for lithium battery applications. The effect of inclusion of 1 to 33 mol% lithium tetrafluoroborate, LiBF(4), into [C2mpyr][BF(4)] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, cyclic voltammetry and cycling of full Li|LiFePO(4) batteries. The increases in ionic conductivity by orders of magnitude observed at higher temperature are most likely associated with an increase in Li ion mobility in the highest plastic phase. At concentrations >5 mol% LiBF(4) the ionic conductivity of these solid-state composites is comparable to the ionic conductivity of room temperature ionic liquids. Galvanostatic cycling of Li|Li symmetrical cells showed that the reversibility of the lithium metal redox reaction at the interface of this plastic crystal electrolyte is sufficient for lithium battery applications. For the first time we demonstrate an all solid state lithium battery incorporating solid electrolytes based on IOPC as opposed to conventional flammable organic solvents.

  3. Development of bulk-type all-solid-state lithium-sulfur battery using LiBH{sub 4} electrolyte

    SciTech Connect

    Unemoto, Atsushi Ikeshoji, Tamio; Yasaku, Syun; Matsuo, Motoaki; Nogami, Genki; Tazawa, Masaru; Taniguchi, Mitsugu; Orimo, Shin-ichi

    2014-08-25

    Stable battery operation of a bulk-type all-solid-state lithium-sulfur battery was demonstrated by using a LiBH{sub 4} electrolyte. The electrochemical activity of insulating elemental sulfur as the positive electrode was enhanced by the mutual dispersion of elemental sulfur and carbon in the composite powders. Subsequently, a tight interface between the sulfur-carbon composite and the LiBH{sub 4} powders was manifested only by cold-pressing owing to the highly deformable nature of the LiBH{sub 4} electrolyte. The high reducing ability of LiBH{sub 4} allows using the use of a Li negative electrode that enhances the energy density. The results demonstrate the interface modification of insulating sulfur and the architecture of an all-solid-state Li-S battery configuration with high energy density.

  4. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    PubMed Central

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-01-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1−xCaxAlO3−δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400–500 °C. The response current value at −300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles. PMID:27886278

  5. Mesoporous silica/ionic liquid quasi-solid-state electrolytes and their application in lithium metal batteries

    NASA Astrophysics Data System (ADS)

    Li, Xiaowei; Zhang, Zhengxi; Yin, Kun; Yang, Li; Tachibana, Kazuhiro; Hirano, Shin-ichi

    2015-03-01

    In this work, the ordered mesoporous silica, SBA-15, is chosen as the matrix for the first time to prepare quasi-solid-state electrolytes (QSSEs) with an ionic liquid, LiTFSI salt and PVdF-HFP. The as-obtained QSSEs are evaluated by electrochemical methods. Lithium metal batteries containing these QSSEs exhibit high discharge capacity and good cycle performance at room temperature, indicating successful battery operation.

  6. Nanoscale electrochemical characterization of a solid-state electrolyte using a manganese-based thin-film probe.

    PubMed

    Liu, Yi-Hung; Liao, Sin-Syu; Haochih Liu, Bernard

    2016-12-08

    A Li-Mn-O thin-film electrode probe has been developed via a facile synthesis process, which enables nanoscale electrochemical investigation of the solid-state electrolyte LiPON. Detailed information of ion transport can be obtained by the thin-film probe, rather than the macroscale electrochemical impedance analysis. It is clarified from the nanoscale analysis that the charge transfer resistance at the Li-Mn-O/LiPON interface dominates the localized impedance, while it can be significantly reduced rather than the electrolyte resistance by applying a DC bias.

  7. Iodine-Pseudohalogen Ionic Liquid-Based Electrolytes for Quasi-Solid-State Dye-Sensitized Solar Cells.

    PubMed

    Lennert, Annkatrin; Sternberg, Michelle; Meyer, Karsten; Costa, Rubén D; Guldi, Dirk M

    2017-10-04

    In the current work, novel symmetrically alkyl-substituted imidazolium-based ionic liquids have been synthesized featuring either iodide (I(-)) or selenocyanate (SeCN(-)) as counteranions. Physicochemical assays based on spectroscopy and electrochemistry techniques have been performed to identify the best ionic liquid for application as electrolytes in quasi-solid-state dye-sensitized solar cells (qssDSSC). The latter were mixed with additives such as 4-tert-butylpyridine (4tbpy) and guanidinium thiocyanate (GuSCN) to optimize electrode surface coverage, ionic diffusion, and dye regeneration. In addition, we demonstrate that electrolytes containing a mixture of I2 and (SeCN)2 enhance the open-circuit voltage of the final quasi-solid-state device by up to 70 mV. As such, iodine-pseudohalogen electrolytes reveal in qssDSSCs a good balance between dye regeneration and hole transport and, in turn, enhance the overall solar energy conversion efficiency by 70% with respect to reference qssDSSCs with iodine-based electrolytes. Finally, devices with the iodine-pseudohalogen electrolyte show a 1000 h stable efficiency of 7-8% under outdoor temperature operation conditions and 1 sun illumination.

  8. Monolayer Solid-State Electrolyte for Electric Double Layer Gating of Graphene Field-Effect Transistors.

    PubMed

    Xu, Ke; Lu, Hao; Kinder, Erich W; Seabaugh, Alan; Fullerton-Shirey, Susan K

    2017-06-27

    The electrostatic gating of graphene field-effect transistors is demonstrated using a monolayer electrolyte. The electrolyte, cobalt crown ether phthalocyanine (CoCrPc) and LiClO4, is deposited as a monolayer on the graphene channel, essentially creating an additional two-dimensional layer on top of graphene. The crown ethers on the CoCrPc solvate lithium ions and the ion location is modulated by a backgate without requiring liquid solvent. Ions dope the channel by inducing image charges; the doping level (i.e., induced charge density) can be modulated by the backgate bias with the extent of the surface potential change being controlled by the magnitude and polarity of the backgate bias. With a crown ether to Li(+) ratio of 5:1, programming tests for which the backgate is held at -VBG shift the Dirac point by ∼15 V, corresponding to a sheet carrier density on the order of 10(12) cm(-2). This charge carrier density agrees with the packing density of monolayer CoCrPc on graphene that would be expected with one Li(+) for every five crown ethers (at the maximum possible Li(+) concentration, 10(13) cm(-2) is predicted). The crown ethers provide two stable states for the Li(+): one near the graphene channel (low-resistance state) and one ∼5 Å away from the channel (high-resistance state). Initial state retention measurements indicate that the two states can be maintained for at least 30 min (maximum time monitored), which is 10(6) times longer than polymer-based electrolytes at room temperature, with at least a 250 Ω μm difference between the channel resistance in the high- and low-resistance states.

  9. A New Miniaturized Inkjet Printed Solid State Electrolyte Sensor for Applications in Life Support Systems - First Results

    NASA Astrophysics Data System (ADS)

    Hill, Christine; Stefanos Fasoulas, -; Eberhart, Martin; Berndt, Felix

    New generations of integrated closed loop systems will combine life support systems (incl. biological components) and energy systems such as fuel cell and electrolysis systems. Those systems and their test beds also contain complex safety sensor monitoring systems. Especially in fuel cells and electrolysis systems, the hydrogen and oxygen flows and exchange into other areas due to diffusion processes or leaks need to be monitored. Knowledge of predominant gas concentrations at all times is essential to avoid explosive gas mixtures. Solid state electrolyte sensors are promising for use as safety sensors. They have already been developed and produced at various institutes, but the power consumption for heating an existing solid state electrolyte sensor element still lies between 1 to 1.5 W and the operational readiness still takes about 20 to 30 s. This is partially due to the current manufacturing process for the solid state electrolyte sensor elements that is based on screen printing technology. However this technology has strong limitations in flexibility of the layout and re-designs. It is therefore suitable for mass production, but not for a flexible development and the production of specific individual sensors, e.g. for space applications. Moreover a disadvantage is the relatively high material consumption, especially in combination with the sensors need of expensive noble metal and ceramic pastes, which leads to a high sensor unit price. The Inkjet technology however opens up completely new possibilities in terms of dimensions, geometries, structures, morphologies and materials of sensors. This new approach is capable of printing finer high-resolution layers without the necessity of meshes or masks for patterning. Using the Inkjet technology a design change is possible at any time on the CAD screen. Moreover the ink is only deposited where it is needed. Custom made sensors, as they are currently demanded in space sensor applications, are thus realized simply

  10. Quantification of the solid-state charge mobility in a model radical polymer

    NASA Astrophysics Data System (ADS)

    Baradwaj, Aditya G.; Rostro, Lizbeth; Alam, Muhammad A.; Boudouris, Bryan W.

    2014-05-01

    We establish that an oft-used radical polymer, poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA), has a solid-state hole mobility value on the order of 10-4 cm2 V-1 s-1 in a space charge-limited device geometry. Despite being completely amorphous and lacking any π-conjugation, these results demonstrate that the hole mobility of PTMA is comparable to many well-studied conjugated polymers [e.g., poly(3-hexylthiophene)]. Furthermore, we show that the space charge-limited charge carrier mobility of these macromolecules is only a weak function of temperature, in contrast to many thermally-activated models of charge transport in polymeric materials. This key result demonstrates that the charge transport in radical polymers is inherently different than that in semicrystalline, conjugated polymers. These results establish the mechanism of solid-state charge transport in radical polymers and provide macromolecular design principles for this emerging class of organic electronic materials.

  11. Quantification of the solid-state charge mobility in a model radical polymer

    SciTech Connect

    Baradwaj, Aditya G.; Rostro, Lizbeth; Boudouris, Bryan W.; Alam, Muhammad A.

    2014-05-26

    We establish that an oft-used radical polymer, poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA), has a solid-state hole mobility value on the order of 10{sup −4} cm{sup 2} V{sup −1} s{sup −1} in a space charge-limited device geometry. Despite being completely amorphous and lacking any π-conjugation, these results demonstrate that the hole mobility of PTMA is comparable to many well-studied conjugated polymers [e.g., poly(3-hexylthiophene)]. Furthermore, we show that the space charge-limited charge carrier mobility of these macromolecules is only a weak function of temperature, in contrast to many thermally-activated models of charge transport in polymeric materials. This key result demonstrates that the charge transport in radical polymers is inherently different than that in semicrystalline, conjugated polymers. These results establish the mechanism of solid-state charge transport in radical polymers and provide macromolecular design principles for this emerging class of organic electronic materials.

  12. Stable, High-Efficiency Pyrrolidinium-Based Electrolyte for Solid-State Dye-Sensitized Solar Cells.

    PubMed

    He, Tong; Wang, Ye Feng; Zeng, Jing Hui

    2015-09-30

    We synthesized a series of pyrrolidinium based dicationic ionic crystals with high melting point and good thermal stability. Research on the crystal structure shows that there are ordered three-dimensional ionic channels in these crystals which is favorable for the ionic conductor to achieve high conductivity and diffusion coefficient. These ionic crystals are applied to electrolyte as matrix in dye sensitized solar cells, and the influence of crystal structure (including the alkylene chain separating two pyrrolidinium rings and anion) versus the device performances are studied by steady-state voltammography, current-voltage trace, and electrochemical impedance spectroscopy. As the solid state electrolyte, an optimized efficiency of 6.02% have achieved under full sunlight irradiation using ionic crystal [C6BEP][TFSI]2. And the device based on this solid electrolyte shows the excellent long-term stability, maintaining 92% of the initial efficiency after 960 h. This study elucidates fundamental the structure of dicationic crystal and provide useful clues for further improvement of solid-state electrolytes in DSSC.

  13. Interfacial behavior of polymer electrolytes

    SciTech Connect

    Kerr, John; Kerr, John B.; Han, Yong Bong; Liu, Gao; Reeder, Craig; Xie, Jiangbing; Sun, Xiaoguang

    2003-06-03

    Evidence is presented concerning the effect of surfaces on the segmental motion of PEO-based polymer electrolytes in lithium batteries. For dry systems with no moisture the effect of surfaces of nano-particle fillers is to inhibit the segmental motion and to reduce the lithium ion transport. These effects also occur at the surfaces in composite electrodes that contain considerable quantities of carbon black nano-particles for electronic connection. The problem of reduced polymer mobility is compounded by the generation of salt concentration gradients within the composite electrode. Highly concentrated polymer electrolytes have reduced transport properties due to the increased ionic cross-linking. Combined with the interfacial interactions this leads to the generation of low mobility electrolyte layers within the electrode and to loss of capacity and power capability. It is shown that even with planar lithium metal electrodes the concentration gradients can significantly impact the interfacial impedance. The interfacial impedance of lithium/PEO-LiTFSI cells varies depending upon the time elapsed since current was turned off after polarization. The behavior is consistent with relaxation of the salt concentration gradients and indicates that a portion of the interfacial impedance usually attributed to the SEI layer is due to concentrated salt solutions next to the electrode surfaces that are very resistive. These resistive layers may undergo actual phase changes in a non-uniform manner and the possible role of the reduced mobility polymer layers in dendrite initiation and growth is also explored. It is concluded that PEO and ethylene oxide-based polymers are less than ideal with respect to this interfacial behavior.

  14. A New Phenomenon: Sub-Tg, Solid-State, Plasticity-Induced Bonding in Polymers

    NASA Astrophysics Data System (ADS)

    Padhye, Nikhil; Parks, David M.; Trout, Bernhardt L.; Slocum, Alexander H.

    2017-04-01

    Polymer self-adhesion due to the interdiffusion of macromolecules has been an active area of research for several decades. Here, we report a new phenomenon of sub-Tg, solid-state, plasticity-induced bonding; where amorphous polymeric films were bonded together in a period of time on the order of a second in the solid-state at ambient temperatures, up to 60 K below their glass transition temperature (Tg), by subjecting them to active plastic deformation. Despite the glassy regime, the bulk plastic deformation triggered the requisite molecular mobility of the polymer chains, causing interpenetration across the interfaces held in contact. Quantitative levels of adhesion and the morphologies of the fractured interfaces validated the sub-Tg, plasticity-induced, molecular mobilization causing bonding. No-bonding outcomes (i) during the uniaxial compressive straining of films (a near-hydrostatic setting which strongly limits plastic flow) and (ii) between an ‘elastic’ and a ‘plastic’ film further established the explicit role of plastic deformation in this newly reported sub-Tg solid-state bonding.

  15. A New Phenomenon: Sub-Tg, Solid-State, Plasticity-Induced Bonding in Polymers

    PubMed Central

    Padhye, Nikhil; Parks, David M.; Trout, Bernhardt L.; Slocum, Alexander H.

    2017-01-01

    Polymer self-adhesion due to the interdiffusion of macromolecules has been an active area of research for several decades. Here, we report a new phenomenon of sub-Tg, solid-state, plasticity-induced bonding; where amorphous polymeric films were bonded together in a period of time on the order of a second in the solid-state at ambient temperatures, up to 60 K below their glass transition temperature (Tg), by subjecting them to active plastic deformation. Despite the glassy regime, the bulk plastic deformation triggered the requisite molecular mobility of the polymer chains, causing interpenetration across the interfaces held in contact. Quantitative levels of adhesion and the morphologies of the fractured interfaces validated the sub-Tg, plasticity-induced, molecular mobilization causing bonding. No-bonding outcomes (i) during the uniaxial compressive straining of films (a near-hydrostatic setting which strongly limits plastic flow) and (ii) between an ‘elastic’ and a ‘plastic’ film further established the explicit role of plastic deformation in this newly reported sub-Tg solid-state bonding. PMID:28425498

  16. Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

    SciTech Connect

    Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; Han, Lili; Grillon, Nathanael; Guy-Bouyssou, Delphine; Bouyssou, Emilien; Proust, Marina; Meng, Ying Shirley

    2016-05-30

    All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grew in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.

  17. Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

    SciTech Connect

    Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; Han, Lili; Grillon, Nathanael; Guy-Bouyssou, Delphine; Bouyssou, Emilien; Proust, Marina; Meng, Ying Shirley

    2016-05-30

    All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grew in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.

  18. Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

    NASA Astrophysics Data System (ADS)

    Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; Han, Lili; Grillon, Nathanael; Guy-Bouyssou, Delphine; Bouyssou, Emilien; Proust, Marina; Meng, Ying Shirley

    2016-08-01

    All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte - electrode interfaces will be critical to improve performance. In this study, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grew in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. The stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.

  19. Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers

    NASA Astrophysics Data System (ADS)

    Chandrahalim, Hengky; Fan, Xudong

    2015-12-01

    This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3‧-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3‧-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm2 per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm2 per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip.

  20. Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers

    PubMed Central

    Chandrahalim, Hengky; Fan, Xudong

    2015-01-01

    This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3′-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3′-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm2 per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm2 per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip. PMID:26674508

  1. Reconfigurable Solid-state Dye-doped Polymer Ring Resonator Lasers.

    PubMed

    Chandrahalim, Hengky; Fan, Xudong

    2015-12-17

    This paper presents wavelength configurable on-chip solid-state ring lasers fabricated by a single-mask standard lithography. The single- and coupled-ring resonator hosts were fabricated on a fused-silica wafer and filled with 3,3'-Diethyloxacarbocyanine iodide (CY3), Rhodamine 6G (R6G), and 3,3'-Diethylthiadicarbocyanine iodide (CY5)-doped polymer as the reconfigurable gain media. The recorded lasing threshold was ~220 nJ/mm(2) per pulse for the single-ring resonator laser with R6G, marking the lowest threshold shown by solid-state dye-doped polymer lasers fabricated with a standard lithography process on a chip. A single-mode lasing from a coupled-ring resonator system with the lasing threshold of ~360 nJ/mm(2) per pulse was also demonstrated through the Vernier effect. The renewability of the dye-doped polymer was examined by removing and redepositing the dye-doped polymer on the same resonator hosts for multiple cycles. We recorded consistent emissions from the devices for all trials, suggesting the feasibility of employing this technology for numerous photonic and biochemical sensing applications that entail for sustainable, reconfigurable, and low lasing threshold coherent light sources on a chip.

  2. Novel Organic-Inorganic Hybrid Electrolyte to Enable LiFePO4 Quasi-Solid-State Li-Ion Batteries Performed Highly around Room Temperature.

    PubMed

    Tan, Rui; Gao, Rongtan; Zhao, Yan; Zhang, Mingjian; Xu, Junyi; Yang, Jinlong; Pan, Feng

    2016-11-16

    A novel type of organic-inorganic hybrid polymer electrolytes with high electrochemical performances around room temperature is formed by hybrid of nanofillers, Y-type oligomer, polyoxyethylene and Li-salt (PBA-Li), of which the Tg and Tm are significantly lowered by blended heterogeneous polyethers and embedded nanofillers with benefit of the dipole modification to achieve the high Li-ion migration due to more free-volume space. The quasi-solid-state Li-ion batteries based on the LiFePO4/15PBA-Li/Li-metal cells present remarkable reversible capacities (133 and 165 mAh g(-1) @0.2 C at 30 and 45 °C, respectively), good rate ability and stable cycle performance (141.9 mAh g(-1) @0.2 C at 30 °C after 150 cycles).

  3. Compact Ozone Differential Absorption Lidar (DIAL) Transmitter Using Solid-State Dye Polymers

    NASA Technical Reports Server (NTRS)

    Jones, Alton L., Jr.; DeYoung, Russell J.; Elsayid-Ele, Hani

    2001-01-01

    A new potential DIAL laser transmitter is described that uses solid-state dye laser materials to make a simpler, more compact, lower mass laser system. Two solid-state dye laser materials were tested to evaluate their performance in a laser oscillator cavity end pumped by a pulsed Nd:YAG laser at 532 nm. The polymer host polymethyl-methacrylate was injected with a pyrromethene laser dye, PM 580, or PM 597. A narrowband laser oscillator cavity was constructed to produce visible wavelengths of 578 and 600 nm which were frequency doubled into the UV region (299 or 300 nm) by using a BBO crystal, resulting in a maximum energy of 11 mJ at a wavelength of 578 nm when pumped by the Nd:YAG laser at an energy of 100 mJ (532 nm). A maximum output energy of 378 microJ was achieved in the UV region at a wavelength of 289 nm but lasted only 2000 laser shots at a repetition rate of 10 Hz. The results are promising and show that a solid-state dye laser based ozone DIAL system is possible with improvements in the design of the laser transmitter.

  4. Polymer electrolyte membrane resistance model

    NASA Astrophysics Data System (ADS)

    Renganathan, Sindhuja; Guo, Qingzhi; Sethuraman, Vijay A.; Weidner, John W.; White, Ralph E.

    A model and an analytical solution for the model are presented for the resistance of the polymer electrolyte membrane of a H 2/O 2 fuel cell. The solution includes the effect of the humidity of the inlet gases and the gas pressure at the anode and the cathode on the membrane resistance. The accuracy of the solution is verified by comparison with experimental data. The experiments were carried out with a Nafion 112 membrane in a homemade fuel cell test station. The membrane resistances predicted by the model agree well with those obtained during the experiments.

  5. Quasi Solid Polymer Electrolytes for Dye Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Dissanayake, M. A. K. Lakshman

    2013-07-01

    Dye-sensitized solar cell (DSSC) has been considered as an alternative to the conventional silicon solar cell because of low cost, easy fabrication and relatively high conversion efficiency. A DSSC consists of a dye-sensitized nanoparticulated TiO2 electrode, an electrolyte containing redox couple and a Pt coated counter electrode. Such solar cells based on an I-/I3- redox couple in an organic solvent usually have conversion efficiencies reaching around 11%. However, a major drawback of these solution based solar cells, originally developed by Gratzel and coworkers is the lack of long-term stability due to liquid leakage, usage of volatile liquids such as acetonitrile, electrode corrosion, and photodecomposition of the dye in the solvent medium. Therefore considerable research efforts have been made in recent years to replace the liquid electrolytes with solid polymer or quasi-solid polymer (gel) electrolytes. Among these approaches, the use of gel polymer electrolytes appears to give rise to successful results in terms of conversion efficiency. Conventional poly (ethylene oxide)(PEO)-based solid polymer electrolytes exhibit poor ionic conductivities at room temperature, which is not sufficient for practical applications. Therefore, most of the recent studies have been directed to the preparation and characterization of gel polymer electrolytes which exhibit higher ionic conductivity at ambient temperature while maintain quai-solid structure. These gel polymer electrolytes prepared by incorporating a liquid electrolyte into a matrix polymer such as polyacrylonitrile(PAN), poly(vinylidene fluoride)(PVdF), poly (methyl methacrylate) (PMMA) and PEO have been employed in quasi-solid-state DSSCs to achieve power conversion efficiencies of more than 5%. Significant improvements have been achieved in recent years by modifications of the electrolytes by optimizing the ionic salt, introducing additives such as inorganic nanofillers, organic molecules and ionic liquids in

  6. Enhancement of phosphorescence and unimolecular behavior in the solid state by perfect insulation of platinum-acetylide polymers.

    PubMed

    Masai, Hiroshi; Terao, Jun; Makuta, Satoshi; Tachibana, Yasuhiro; Fujihara, Tetsuaki; Tsuji, Yasushi

    2014-10-22

    Controlling the thermal fluctuations and molecular environment of a phosphorescent polymer backbone is vital to enhancing its phosphorescence intensity in the solid state. Here, we demonstrate enhanced phosphorescence control through a systematic investigation of cyclodextrin-based insulated platinum-acetylide polymers with well-defined coverage areas. Modification of the coverage areas revealed two unprecedented effects of macrocyclic insulation on phosphorescence behavior. First, the insulation of particular areas suppresses the thermal relaxation processes of the triplet species because of the restriction of structural fluctuations. Cyclic insulation fixes a polymer chain and concomitantly enhances the phosphorescence intensity in both the solution and solid states. Second, complete three-dimensional insulation protects the polymer from interactions with other platinum and acetylide units, and even oxygen molecules. Notably, these polymers display identical phosphorescence behaviors in both the solution and solid states, essentially achieving "unimolecular phosphorescence."

  7. Dynamics of benzimidazole ethylphosphonate: a solid-state NMR study of anhydrous composite proton-conducting electrolytes.

    PubMed

    Yan, Z Blossom; De Almeida, Nicole E; Traer, Jason W; Goward, Gillian R

    2013-11-07

    Imidazole phosphate and phosphonate solid acids model the hydrogen-bonding networks and dynamics of the anhydrous electrolyte candidate for proton exchange membrane fuel cells. Solid-state NMR reveals that phosphate and phosphonate anion dynamics dominate the rate of long-range proton transport, and that the presence of a membrane host facilitates proton mobility, as evidenced by a decreased correlation time of the composites (80 ± 15 ms) relative to the pristine salt (101 ± 5 ms). Benzimidazole ethylphosphonate (Bi-ePA) is chosen as a model salt to investigate the membrane system. The hydrogen-bonding structure of Bi-ePA is established using X-ray diffraction coupled with solid-state (1)H-(1)H DQC NMR. The anion dynamics has been determined using solid-state (31)P CODEX NMR. By comparing the dynamics of ethylphosphonate groups in pristine salt and membrane-salt composites, it is clear that the rotation process involves three-site exchange. Through data interpretation, a stretched exponential function is introduced with the stretching exponent, β, ranging 0 < β ≤ 1. The (31)P CODEX data for pristine salt are fitted with single exponential decay where β = 1; however, the data for the membrane-salt composites are fitted with stretched exponential functions, where β has a constant value of 0.5. This β value suggests a non-Gaussian distribution of the dynamic systems in the composite sample, which is introduced by the membrane host.

  8. Quasi-solid state electrolyte for semi-transparent bifacial dye-sensitized solar cell with over 10% power conversion efficiency

    NASA Astrophysics Data System (ADS)

    Hwang, Dae-Kue; Nam, Jung Eun; Jo, Hyo Jeong; Sung, Shi-Joon

    2017-09-01

    In traditional dye-sensitized solar cells (DSSCs), the liquid electrolyte (LE) presents a problem for long-term stability. Herein, we demonstrate a bifacial DSSC by combining a new metal-free organic dye and a quasi-solid state electrolyte (QSSE) that contains poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP)-based polymer gel. The incident light irradiates the front side of the DSSC, and the transmitted light is reused after reflection on the back side. Owing to the semi-transparent DSSC electrode, the reflected light can penetrate and be absorbed by the dye molecules in the DSSC, thereby enhancing the short-circuit current density and thus the overall power conversion efficiency (PCE). The PCE for the DSSC device with QSSE from bifacial irradiation is 10.37%, a value that is comparable to that obtained with LE-based DSSC (9.89%). The stability of the device is enhanced when the polymer gel containing PVdF-HFP is mixed with the LE, and the effectiveness of PVdF-HFP as a gelator is attributed to its interaction with the Li+ ions. Based on our preliminary results, this architecture can lead to more stable bifacial QSSE-based DSSCs without sacrificing the photovoltaic performance.

  9. Nanocomposite polymer electrolyte for rechargeable magnesium batteries

    SciTech Connect

    Shao, Yuyan; Rajput, Nav Nidhi; Hu, Jian Z.; Hu, Mary Y.; Liu, Tianbiao L.; Wei, Zhehao; Gu, Meng; Deng, Xuchu; Xu, Suochang; Han, Kee Sung; Wang, Jiulin; Nie, Zimin; Li, Guosheng; Zavadil, K.; Xiao, Jie; Wang, Chong M.; Henderson, Wesley A.; Zhang, Jiguang; Wang, Yong; Mueller, Karl T.; Persson, Kristin A.; Liu, Jun

    2014-12-28

    Nanocomposite polymer electrolytes present new opportunities for rechargeable magnesium batteries. However, few polymer electrolytes have demonstrated reversible Mg deposition/dissolution and those that have still contain volatile liquids such as tetrahydrofuran (THF). In this work, we report a nanocomposite polymer electrolyte based on poly(ethylene oxide) (PEO), Mg(BH4)2 and MgO nanoparticles for rechargeable Mg batteries. Cells with this electrolyte have a high coulombic efficiency of 98% for Mg plating/stripping and a high cycling stability. Through combined experiment-modeling investigations, a correlation between improved solvation of the salt and solvent chain length, chelation and oxygen denticity is established. Following the same trend, the nanocomposite polymer electrolyte is inferred to enhance the dissociation of the salt Mg(BH4)2 and thus improve the electrochemical performance. The insights and design metrics thus obtained may be used in nanocomposite electrolytes for other multivalent systems.

  10. A solid-state NMR method to determine domain sizes in multi-component polymer formulations

    NASA Astrophysics Data System (ADS)

    Schlagnitweit, Judith; Tang, Mingxue; Baias, Maria; Richardson, Sara; Schantz, Staffan; Emsley, Lyndon

    2015-12-01

    Polymer domain sizes are related to many of the physical properties of polymers. Here we present a solid-state NMR experiment that is capable of measuring domain sizes in multi-component mixtures. The method combines selective excitation of carbon magnetization to isolate a specific component with proton spin diffusion to report on domain size. We demonstrate the method in the context of controlled release formulations, which represents one of today's challenges in pharmaceutical science. We show that we can measure domain sizes of interest in the different components of industrial pharmaceutical formulations at natural isotopic abundance containing various (modified) cellulose derivatives, such as microcrystalline cellulose matrixes that are film-coated with a mixture of ethyl cellulose (EC) and hydroxypropyl cellulose (HPC).

  11. Electrodeposited polyethylenedioxythiophene with infiltrated gel electrolyte interface: a close contest of an all-solid-state supercapacitor with its liquid-state counterpart.

    PubMed

    Anothumakkool, Bihag; Torris A T, Arun; Bhange, Siddheshwar N; Badiger, Manohar V; Kurungot, Sreekumar

    2014-06-07

    We report the design of an all-solid-state supercapacitor, which has charge storage characteristics closely matching that of its liquid-state counterpart even under extreme temperature and humidity conditions. The prototype is made by electro-depositing polyethylenedioxythiophene (PEDOT) onto the individual carbon fibers of a porous carbon substrate followed by intercalating the matrix with polyvinyl alcohol-sulphuric acid (PVA-H2SO4) gel electrolyte. The electrodeposited layer of PEDOT maintained a flower-like growth pattern along the threads of each carbon fiber. This morphology and the alignment of PEDOT led to an enhanced surface area and electrical conductivity, and the pores in the system enabled effective intercalation of the polymer-gel electrolyte. Thus, the established electrode-electrolyte interface nearly mimics that of its counterpart based on the liquid electrolyte. Consequently, the solid device attained very low internal resistance (1.1 Ω cm(-2)) and a high specific capacitance (181 F g(-1)) for PEDOT at a discharge current density of 0.5 A g(-1). Even with a high areal capacitance of 836 mF cm(-2) and volumetric capacitance of 28 F cm(-3), the solid device retained a mass-specific capacitance of 111 F g(-1) for PEDOT. This is in close agreement with the value displayed by the corresponding liquid-state system (112 F g(-1)), which was fabricated by replacing the gel electrolyte with 0.5 M H2SO4. The device also showed excellent charge-discharge stability for 12 000 cycles at 5 A g(-1). The performance of the device was consistent even under wide-ranging humidity (30-80%) and temperature (-10 to 80 °C) conditions. Finally, a device fabricated by increasing the electrode area four times was used to light an LED, which validated the scalability of the process.

  12. Magnesium Ethylenediamine Borohydride as Solid-State Electrolyte for Magnesium Batteries.

    PubMed

    Roedern, Elsa; Kühnel, Ruben-Simon; Remhof, Arndt; Battaglia, Corsin

    2017-04-07

    Solid-state magnesium ion conductors with exceptionally high ionic conductivity at low temperatures, 5 × 10(-8) Scm(-1) at 30 °C and 6 × 10(-5) Scm(-1) at 70 °C, are prepared by mechanochemical reaction of magnesium borohydride and ethylenediamine. The coordination complexes are crystalline, support cycling in a potential window of 1.2 V, and allow magnesium plating/stripping. While the electrochemical stability, limited by the ethylenediamine ligand, must be improved to reach competitive energy densities, our results demonstrate that partially chelated Mg(2+) complexes represent a promising platform for the development of an all-solid-state magnesium battery.

  13. Magnesium Ethylenediamine Borohydride as Solid-State Electrolyte for Magnesium Batteries

    NASA Astrophysics Data System (ADS)

    Roedern, Elsa; Kühnel, Ruben-Simon; Remhof, Arndt; Battaglia, Corsin

    2017-04-01

    Solid-state magnesium ion conductors with exceptionally high ionic conductivity at low temperatures, 5 × 10-8 Scm-1 at 30 °C and 6 × 10-5 Scm-1 at 70 °C, are prepared by mechanochemical reaction of magnesium borohydride and ethylenediamine. The coordination complexes are crystalline, support cycling in a potential window of 1.2 V, and allow magnesium plating/stripping. While the electrochemical stability, limited by the ethylenediamine ligand, must be improved to reach competitive energy densities, our results demonstrate that partially chelated Mg2+ complexes represent a promising platform for the development of an all-solid-state magnesium battery.

  14. Magnesium Ethylenediamine Borohydride as Solid-State Electrolyte for Magnesium Batteries

    PubMed Central

    Roedern, Elsa; Kühnel, Ruben-Simon; Remhof, Arndt; Battaglia, Corsin

    2017-01-01

    Solid-state magnesium ion conductors with exceptionally high ionic conductivity at low temperatures, 5 × 10−8 Scm−1 at 30 °C and 6 × 10−5 Scm−1 at 70 °C, are prepared by mechanochemical reaction of magnesium borohydride and ethylenediamine. The coordination complexes are crystalline, support cycling in a potential window of 1.2 V, and allow magnesium plating/stripping. While the electrochemical stability, limited by the ethylenediamine ligand, must be improved to reach competitive energy densities, our results demonstrate that partially chelated Mg2+ complexes represent a promising platform for the development of an all-solid-state magnesium battery. PMID:28387305

  15. High-performance flexible all-solid-state microbatteries based on solid electrolyte of lithium boron oxynitride

    NASA Astrophysics Data System (ADS)

    Song, Seung-Wan; Lee, Ki-Chang; Park, Ho-Young

    2016-10-01

    Rapidly growing interest and demand for wearable electronics require the development of flexible and lightweight all-solid-state batteries as power sources that guarantee high performance and safety with the absence of the risk of fire or explosion that can occur with traditional liquid electrolyte systems. Herein, we successfully fabricate new flexible all-solid-state microbatteries integrating a solid electrolyte film of lithium boron oxynitride (LiBON) on a flexible substrate using sophisticated thin-film fabrication technology. The new microbattery of Li/LiBON/LiCoO2 exhibits excellent mechanical integrity even under severe bending and twisting test conditions, enabling the realization of flexible microbatteries. The microbatteries demonstrate superior electrochemical cycling stability relative to conventional batteries, delivering an outstanding capacity retention of 90% on the 1000th cycle. Furthermore, operation at various temperatures from -10 °C to +60 °C and fast charging within 3-6 min are achieved. With various types of flexible substrates, the microbatteries can provide diverse opportunities for flexible and wearable electronics.

  16. Reducing Interfacial Resistance between Garnet-Structured Solid-State Electrolyte and Li-Metal Anode by a Germanium Layer.

    PubMed

    Luo, Wei; Gong, Yunhui; Zhu, Yizhou; Li, Yiju; Yao, Yonggang; Zhang, Ying; Fu, Kun Kelvin; Pastel, Glenn; Lin, Chuan-Fu; Mo, Yifei; Wachsman, Eric D; Hu, Liangbing

    2017-06-01

    Substantial efforts are underway to develop all-solid-state Li batteries (SSLiBs) toward high safety, high power density, and high energy density. Garnet-structured solid-state electrolyte exhibits great promise for SSLiBs owing to its high Li-ion conductivity, wide potential window, and sufficient thermal/chemical stability. A major challenge of garnet is that the contact between the garnet and the Li-metal anodes is poor due to the rigidity of the garnet, which leads to limited active sites and large interfacial resistance. This study proposes a new methodology for reducing the garnet/Li-metal interfacial resistance by depositing a thin germanium (Ge) (20 nm) layer on garnet. By applying this approach, the garnet/Li-metal interfacial resistance decreases from ≈900 to ≈115 Ω cm(2) due to an alloying reaction between the Li metal and the Ge. In agreement with experiments, first-principles calculation confirms the good stability and improved wetting at the interface between the lithiated Ge layer and garnet. In this way, this unique Ge modification technique enables a stable cycling performance of a full cell of lithium metal, garnet electrolyte, and LiFePO4 cathode at room temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Alkaline composite PEO-PVA-glass-fibre-mat polymer electrolyte for Zn-air battery

    NASA Astrophysics Data System (ADS)

    Yang, Chun-Chen; Lin, Sheng-Jen

    An alkaline composite PEO-PVA-glass-fibre-mat polymer electrolyte with high ionic conductivity (10 -2 S cm -1) at room temperature has been prepared and applied to solid-state primary Zn-air batteries. The electrolyte shows excellent mechanical strength. The electrochemical characteristics of the batteries were experimentally investigated by means of ac impedance spectroscopy and galvanostatic discharge. The results indicate that the PEO-PVA-glass-fibre-mat composite polymer electrolyte is a promising candidate for application in alkaline primary Zn-air batteries.

  18. Solid state drug-polymer miscibility studies using the model drug ABT-102.

    PubMed

    Jog, Rajan; Gokhale, Rajeev; Burgess, Diane J

    2016-07-25

    Amorphous solid dispersions typically suffer storage stability issues due to: their amorphous nature, high drug loading, uneven drug:stabilizer ratio and plasticization effects as a result of hygroscopic excipients. An extensive solid state miscibility study was conducted to aid in understanding the mechanisms involved in drug/stabilizer interactions. ABT-102 (model drug) and nine different polymers with different molecular weights and viscosities were selected to investigate drug/polymer miscibility. Three different polymer:drug ratios (1:3, 1:1 and 3:1, w/w) were analyzed using: DSC, FTIR and PXRD. Three different techniques were used to prepare the amorphous solid dispersions: serial dilution, solvent evaporation and spray drying. Spray drying was the best method to obtain amorphous solid dispersions. However, under certain conditions amorphous formulations could be obtained using solvent evaporation. Melting point depression was used to calculate interaction parameters and free energy of mixing for the various drug polymer mixtures. The spray dried solid dispersions yielded a negative free energy of mixing which indicated strong drug-polymer miscibility compared to the solvent evaporation and serial dilution method. Soluplus was the best stabilizer compared to PVP and HPMC, which is probably a consequence of strong hydrogen bonding between the two CO moieties of soluplus and the drug NH moieities. Copyright © 2016. Published by Elsevier B.V.

  19. Decoupling Mechanical and Ion Transport Properties in Polymer Electrolyte Membranes

    NASA Astrophysics Data System (ADS)

    McIntosh, Lucas D.

    Polymer electrolytes are mixtures of a polar polymer and salt, in which the polymer replaces small molecule solvents and provides a dielectric medium so that ions can dissociate and migrate under the influence of an external electric field. Beginning in the 1970s, research in polymer electrolytes has been primarily motivated by their promise to advance electrochemical energy storage and conversion devices, such as lithium ion batteries, flexible organic solar cells, and anhydrous fuel cells. In particular, polymer electrolyte membranes (PEMs) can improve both safety and energy density by eliminating small molecule, volatile solvents and enabling an all-solid-state design of electrochemical cells. The outstanding challenge in the field of polymer electrolytes is to maximize ionic conductivity while simultaneously addressing orthogonal mechanical properties, such as modulus, fracture toughness, or high temperature creep resistance. The crux of the challenge is that flexible, polar polymers best-suited for polymer electrolytes (e.g., poly(ethylene oxide)) offer little in the way of mechanical robustness. Similarly, polymers typically associated with superior mechanical performance (e.g., poly(methyl methacrylate)) slow ion transport due to their glassy polymer matrix. The design strategy is therefore to employ structured electrolytes that exhibit distinct conducting and mechanically robust phases on length scales of tens of nanometers. This thesis reports a remarkably simple, yet versatile synthetic strategy---termed polymerization-induced phase separation, or PIPS---to prepare PEMs exhibiting an unprecedented combination of both high conductivity and high modulus. This performance is enabled by co-continuous, isotropic networks of poly(ethylene oxide)/ionic liquid and highly crosslinked polystyrene. A suite of in situ, time-resolved experiments were performed to investigate the mechanism by which this network morphology forms, and it appears to be tied to the

  20. Overcoming sustainability and energy challenges in polymer science via solid-state shear pulverization

    NASA Astrophysics Data System (ADS)

    Brunner, Philip

    Solid-state shear pulverization (SSSP) is an innovative, continuous, environmentally benign, and industrially scalable process used to make materials that cannot be made via conventional processing techniques, reduce material cost by eliminating processing steps, and/or produce materials with superior properties as a result of better break-up and dispersion of additives. The SSSP process employs a modified twin-screw extruder in which the barrels are cooled rather than heated. This allows for high shear and compressive forces on the material during operation, which results in repeated fragmentation and fusion steps in the solid state. Technologically, this thesis provides the first in-depth study of the concept of specific energy in SSSP and how this variable can be tailored to optimize the end-properties while lowering costs for processing homopolymer, blend, or polymer composite systems. Furthermore, this thesis demonstrates the successful injection molding of SSSP-processed materials. An 80/20 wt% polypropylene (PP) and microcrystalline cellulose composite was manufactured with SSSP and injection molded into a bottle cap. These caps showed major benefits over neat PP such as increased stiffness and reduction in oxygen permeability. Finally, a description is provided of how SSSP can be used as a one-step solid-state compounding process that can add color, UV stabilizers, anti-statics, and other processing aids to polymer and uniformly and effectively disperses them in the polymer while pulverizing to a fine powder for roto-molding. Scientifically, process-structure-property relationships are investigated in detail with several homopolymers. The SSSP process is used to disperse heterogeneous nucleation agents (naturally found in commercial pellets) in the polymer. This led to major structural changes such as an increase in crystallizability and crystallinity for poly(lactic acid) (PLA) and in rigid amorphous fraction (RAF) at constant crystallinity for Nylon 11

  1. Ionic conductivity measurement in magnesium aluminate spinel and solid state galvanic cell with magnesium aluminate electrolyte

    NASA Astrophysics Data System (ADS)

    Lee, Myongjai

    This thesis work is about the experimental measurement of electronic and ionic conductivities in the MgAl2O4 spinel at 500˜600°C range and exploring the fundamental origin of solid-state galvanic cell behavior in the cell of Al|MgAl2O4|Mg, Al|MgAl2O 4|C, and Mg|MgAl2O4|C, in which at least one metal electrode in common with the composition of the electrolyte. For the electronic conductivity measurement, we have used the ion-blocking Gold and Carbon electrodes which are inert with both Mg and Al ions to suppress the ionic conduction from the total conduction. DC polarization method was used to measure the conduction through Au|MgAl2O4|Au and C|MgAl2O4|C specimens. The measured electrical conductivity using Au|MgAl2O4|Au and C|MgAl2O4|C specimens showed 10-9.3 ˜ 10-8.4 (O·cm) -1 at 600˜720°C range following the Arrhenius-type relation. These conductivity data are in agreement with reported data obtained from Pt and Ag ion-blocking electrodes deposited on MgAl2O4 specimens. For the ionic conductivity measurement, we have used the non-blocking Al and Mg electrodes for Al and Mg ionic conductivities, respectively. Ionic conductivity measurement of Al and Mg in separate manner has not been reported yet. In both Al|MgAl2O4|Al and Mg|MgAl2O 4|Mg specimens, gradual increase of conduction was observed once at the initial period before it reaches the steady state conduction. By DC method on the range of 580˜650°C, steady state Al ionic conductivity was measured from Al|MgAl2O4|Al specimen showing 10 -7.7 ˜ 10-6.8 (O·cm)-1 with the activation energy of 1.9eV in sigma = sigma0 exp-QRT formula. There was no difference in the conductivity by the change of the atmosphere from 5%H2 + 95%N2 mixed gas to pure Ar gas. So it was confirmed that the oxygen defect chemistry did not play a role. For Mg ionic conductivity Mg|MgAl2O4|Mg specimen was used and the measured conductivity shows 10-6.7 ˜ 10-4.4 (O·cm)-1 at 400˜550°C with the activation energy of 1.44eV at Ar gas

  2. First Principles Study of Electrochemical and Chemical Stability of the Solid Electrolyte-Electrode Interfaces in All-Solid-State Li-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Yizhou; He, Xingfeng; Mo, Yifei

    All-solid-state Li-ion battery is a promising next-generation energy-storage technology. Using novel ceramic solid electrolyte materials, all-solid-state battery has advantages of intrinsic safety and high energy density compared to current Li-ion batteries based on organic liquid electrolyte. However, the power density achieved in all-solid-state battery is still unsatisfactory. The high interfacial resistance at electrode-electrolyte interface is one of the major limiting factors. Here we demonstrated a computational approach based on first principles calculation to systematically investigate the chemical and electrochemical stability of solid electrolyte materials, and provide insightful understanding of the degradation and passivation mechanisms at the interface. Our calculation revealed that the intrinsic stability of solid electrolyte materials and solid electrolyte-electrode interfaces is limited and the formation of interphase layers are thermodynamically favorable. Our study demonstrated a computational scheme to evaluate the electrochemical and chemical stability of the solid interfaces. Our newly gained understanding provided principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries. This work was supported by Office of Energy Efficiency and Renewable Energy (DE-EE0006860).

  3. HCN polymers characterized by SSNMR: Solid state reaction of crystalline tetramer (diaminomaleonitrile)

    NASA Astrophysics Data System (ADS)

    Mamajanov, Irena; Herzfeld, Judith

    2009-04-01

    The HCN tetramer, diaminomaleonitrile, crystallizes in sheets with amine and nitrile groups of neighboring molecules in close proximity. This suggests the possibility of relatively facile acid-base addition to form a protopeptide polymer. We find that moderate heating under argon indeed results in an unmistakable reaction, with the abrupt transformation of pale crystallites to shrunken dark particles that become electrically conductive upon doping with iodine. Since nearly a quarter of the mass is lost in the process and the released gas condenses, polymerizes, and reacts with aqueous AgNO3 like HCN, it seems likely that the dark solid is a polymer of HCN trimer. C13 and N15 solid state NMR spectra show the formation of new N-C bonds, and entirely different functional groups from those observed in polymers formed by liquid HCN. These include three different types of nitrogen functionalities and an absence of saturated carbon or nitrile. The observed chemical shifts, optical properties, and electrical conductivity are consistent with polymers of HCN trimer that have undergone cyclization to form poly-[aminoimidazole].

  4. HCN polymers characterized by SSNMR: Solid state reaction of crystalline tetramer (diaminomaleonitrile)

    PubMed Central

    Mamajanov, Irena; Herzfeld, Judith

    2009-01-01

    The HCN tetramer, diaminomaleonitrile, crystallizes in sheets with amine and nitrile groups of neighboring molecules in close proximity. This suggests the possibility of relatively facile acid-base addition to form a protopeptide polymer. We find that moderate heating under argon indeed results in an unmistakable reaction, with the abrupt transformation of pale crystallites to shrunken dark particles that become electrically conductive upon doping with iodine. Since nearly a quarter of the mass is lost in the process and the released gas condenses, polymerizes, and reacts with aqueous AgNO3 like HCN, it seems likely that the dark solid is a polymer of HCN trimer. 13C and 15N solid state NMR spectra show the formation of new N–C bonds, and entirely different functional groups from those observed in polymers formed by liquid HCN. These include three different types of nitrogen functionalities and an absence of saturated carbon or nitrile. The observed chemical shifts, optical properties, and electrical conductivity are consistent with polymers of HCN trimer that have undergone cyclization to form poly-[aminoimidazole]. PMID:19355748

  5. Plating a Dendrite-Free Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte.

    PubMed

    Zhou, Weidong; Wang, Shaofei; Li, Yutao; Xin, Sen; Manthiram, Arumugam; Goodenough, John B

    2016-08-03

    A cross-linked polymer containing pendant molecules attached to the polymer framework is shown to form flexible and low-cost membranes, to be a solid Li(+) electrolyte up to 270 °C, much higher than those based on poly(ethylene oxide), to be wetted by a metallic lithium anode, and to be not decomposed by the metallic anode if the anions of the salt are blocked by a ceramic electrolyte in a polymer/ceramic membrane/polymer sandwich electrolyte (PCPSE). In this sandwich architecture, the double-layer electric field at the Li/polymer interface is reduced due to the blocked salt anion transfer. The polymer layer adheres/wets the lithium metal surface and makes the Li-ion flux at the interface more homogeneous. This structure integrates the advantages of the ceramic and polymer. With the PCPSE, all-solid-state Li/LiFePO4 cells showed a notably high Coulombic efficiency of 99.8-100% over 640 cycles.

  6. Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR

    NASA Astrophysics Data System (ADS)

    Deschamps, Michaël; Gilbert, Edouard; Azais, Philippe; Raymundo-Piñero, Encarnación; Ammar, Mohammed Ramzi; Simon, Patrick; Massiot, Dominique; Béguin, François

    2013-04-01

    Supercapacitors are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions. Insight into the molecular mechanisms at work inside supercapacitor carbon electrodes is obtained with 13C and 11B ex situ magic-angle spinning nuclear magnetic resonance (MAS-NMR). In activated carbons soaked with an electrolyte solution, two distinct adsorption sites are detected by NMR, both undergoing chemical exchange with the free electrolyte molecules. On charging, anions are substituted by cations in the negative carbon electrode and cations by anions in the positive electrode, and their proportions in each electrode are quantified by NMR. Moreover, acetonitrile molecules are expelled from the adsorption sites at the negative electrode alone. Two nanoporous carbon materials were tested, with different nanotexture orders (using Raman and 13C MAS-NMR spectroscopies), and the more disordered carbon shows a better capacitance and a better tolerance to high voltages.

  7. Tailoring the physical properties of homopolymers and polymer nanocomposites via solid-state processing

    NASA Astrophysics Data System (ADS)

    Pierre, Cynthia

    Numerous approaches can be used to modify polymer properties. In this thesis, it is demonstrated that an innovative, continuous, industrially scalable process called solid-state shear pulverization (SSSP) can be used to enhance polymer properties with and without the addition of nanofillers. The SSSP process employs a modified twin-screw extruder in which the barrel is cooled rather than heated, resulting in the polymer being processed at a temperature below its glass transition temperature, if the polymer is amorphous, or its melt transition temperature, if the polymer is semi-crystalline. The material processed via SSSP experiences high levels of shear and compressive stresses, resulting in many repeated fragmentation and fusion steps during pulverization, which can lead to mechanochemistry. This research provides the first in-depth study on the effect of SSSP processing on the molecular structure as well as physical properties of homopolymers. Rheological characterization has demonstrated an increase in the melt viscosity of pulverized poly(ethylene terephthalate) (PET), which can be ascribed to the in situ formation of lightly branched PET. Further evidence of branched PET is provided via a dramatic increase in the rate of crystallization of the pulverized samples. These results suggest that SSSP processing can enhance the reuse and recyclability of PET. While SSSP processing has dramatic effects on the structure of polyesters and consequently their properties, a mild effect is observed for polyolefins. This thesis also demonstrates via a combination of methods that the well-exfoliated state can be achieved via SSSP processing of various polymer nanocomposites, using as-received, unmodified fillers. For example, extensive comparisons are made concerning the thermal stability in air or nitrogen atmosphere of polypropylene (PP)/clay, PP/graphite, and PP/carbon nanotube (CNT) nanocomposites made by SSSP. These comparisons suggest that the mechanism by which CNTs

  8. Brownian dynamics of a protein-polymer chain complex in a solid-state nanopore

    NASA Astrophysics Data System (ADS)

    Wells, Craig C.; Melnikov, Dmitriy V.; Gracheva, Maria E.

    2017-08-01

    We study the movement of a polymer attached to a large protein inside a nanopore in a thin silicon dioxide membrane submerged in an electrolyte solution. We use Brownian dynamics to describe the motion of a negatively charged polymer chain of varying lengths attached to a neutral protein modeled as a spherical bead with a radius larger than that of the nanopore, allowing the chain to thread the nanopore but preventing it from translocating. The motion of the protein-polymer complex within the pore is also compared to that of a freely translocating polymer. Our results show that the free polymer's standard deviations in the direction normal to the pore axis is greater than that of the protein-polymer complex. We find that restrictions imposed by the protein, bias, and neighboring chain segments aid in controlling the position of the chain in the pore. Understanding the behavior of the protein-polymer chain complex may lead to methods that improve molecule identification by increasing the resolution of ionic current measurements.

  9. Novel polymer electrolyte from poly(carbonate-ether) and lithium tetrafluoroborate for lithium-oxygen battery

    NASA Astrophysics Data System (ADS)

    Lu, Qi; Gao, Yonggang; Zhao, Qiang; Li, Ji; Wang, Xianhong; Wang, Fosong

    2013-11-01

    Novel polymer electrolyte based on low-molecular weight poly(carbonate-ether) and lithium tetrafluoroborate has been prepared and used in lithium-oxygen battery for the first time, the electrolyte with approximate 17% of LiBF4 showed ionic conductivity of 1.57 mS cm-1. Infrared spectra analysis indicates that obvious interaction between the lithium ions and partial oxygen atoms in the host polymer exists, and the lithium salt and the host polymer have good miscibility. The lithium-oxygen battery from this polymer electrolyte shows similar cyclic stability to traditional liquid electrolyte observed by FT-IR, AFM and electrochemical measurements, which may provide a new choice for fabrication of all-solid-state high-capacity rechargeable lithium-oxygen battery with better safety.

  10. Preparation of Li2S-P2S5 solid electrolyte from N-methylformamide solution and application for all-solid-state lithium battery

    NASA Astrophysics Data System (ADS)

    Teragawa, Shingo; Aso, Keigo; Tadanaga, Kiyoharu; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2014-02-01

    Electrode-solid electrolyte composite materials for all-solid-state lithium batteries were prepared by coating of the Li2S-P2S5 solid electrolyte onto LiCoO2 particles using a N-methylformamide (NMF) solution of 80Li2S·20P2S5 (mol%) solid electrolyte. SEM and EDX analysis showed that the Li2S-P2S5 solid electrolyte was uniformly coated on LiCoO2 particles. The all-solid-state cell using the LiCoO2 particles coated with the solid electrolyte showed higher charge-discharge capacity than the cells using uncoated LiCoO2 particles.

  11. Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

    DOE PAGES

    Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; ...

    2016-05-30

    All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grewmore » in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.« less

  12. Molecular dynamics of neutral polymer bonding agent (NPBA) as revealed by solid-state NMR spectroscopy.

    PubMed

    Hu, Wei; Su, Yongchao; Zhou, Lei; Pang, Aimin; Cai, Rulin; Ma, Xingang; Li, Shenhui

    2014-01-22

    Neutral polymer bonding agent (NPBA) is one of the most promising polymeric materials, widely used in nitrate ester plasticized polyether (NEPE) propellant as bonding agent. The structure and dynamics of NPBA under different conditions of temperatures and sample processing are comprehensively investigated by solid state NMR (SSNMR). The results indicate that both the main chain and side chain of NPBA are quite rigid below its glass transition temperature (Tg). In contrast, above the Tg, the main chain remains relatively immobilized, while the side chains become highly flexible, which presumably weakens the interaction between bonding agent and the binder or oxidant fillers and in turn destabilizes the high modulus layer formed around the oxidant fillers. In addition, no obvious variation is found for the microstructure of NPBA upon aging treatment or soaking with acetone. These experimental results provide useful insights for understanding the structural properties of NPBA and its interaction with other constituents of solid composite propellants under different processing and working conditions.

  13. Alkali-Resistant Quasi-Solid-State Electrolyte for Stretchable Supercapacitors.

    PubMed

    Tang, Qianqiu; Wang, Wenqiang; Wang, Gengchao

    2016-10-05

    Research on stretchable energy-storage devices has been motivated by elastic electronics, and considerable research efforts have been devoted to the development of stretchable electrodes. However, stretchable electrolytes, another critical component in stretchable devices, have earned quite little attention, especially the alkali-resistant ones. Here, we reported a novel stretchable alkali-resistant electrolyte made of a polyolefin elastomer porous membrane supported potassium hydroxide-potassium polyacrylate (POE@KOH-PAAK). The as-prepared electrolyte shows a negligible plastic deformation even after 1000 stretching cycles at a strain of 150% as well as a high conductivity of 0.14 S cm(-1). It also exhibits excellent alkali resistance, which shows no obvious degradation of the mechanical performance after immersion in 2 M KOH for up to 2 weeks. To demonstrate its good properties, a high-performance stretchable supercapacitor is assembled using a carbon-nanotube-film-supported NiCo2O4 (CNT@NiCo2O4) as the cathode and Fe2O3 (CNT@Fe2O3) as the anode, proving great application promise of the stretchable alkali-resistant electrolyte in stretchable energy-storage devices.

  14. Solid-state synthesis and mechanical unfolding of polymers of T4 lysozyme

    PubMed Central

    Yang, Guoliang; Cecconi, Ciro; Baase, Walter A.; Vetter, Ingrid R.; Breyer, Wendy A.; Haack, Julie A.; Matthews, Brian W.; Dahlquist, Frederick W.; Bustamante, Carlos

    2000-01-01

    Recent advances in single molecule manipulation methods offer a novel approach to investigating the protein folding problem. These studies usually are done on molecules that are naturally organized as linear arrays of globular domains. To extend these techniques to study proteins that normally exist as monomers, we have developed a method of synthesizing polymers of protein molecules in the solid state. By introducing cysteines at locations where bacteriophage T4 lysozyme molecules contact each other in a crystal and taking advantage of the alignment provided by the lattice, we have obtained polymers of defined polarity up to 25 molecules long that retain enzymatic activity. These polymers then were manipulated mechanically by using a modified scanning force microscope to characterize the force-induced reversible unfolding of the individual lysozyme molecules. This approach should be general and adaptable to many other proteins with known crystal structures. For T4 lysozyme, the force required to unfold the monomers was 64 ± 16 pN at the pulling speed used. Refolding occurred within 1 sec of relaxation with an efficiency close to 100%. Analysis of the force versus extension curves suggests that the mechanical unfolding transition follows a two-state model. The unfolding forces determined in 1 M guanidine hydrochloride indicate that in these conditions the activation barrier for unfolding is reduced by 2 kcal/mol. PMID:10618384

  15. Solid-state synthesis and mechanical unfolding of polymers of T4 lysozyme.

    PubMed

    Yang, G; Cecconi, C; Baase, W A; Vetter, I R; Breyer, W A; Haack, J A; Matthews, B W; Dahlquist, F W; Bustamante, C

    2000-01-04

    Recent advances in single molecule manipulation methods offer a novel approach to investigating the protein folding problem. These studies usually are done on molecules that are naturally organized as linear arrays of globular domains. To extend these techniques to study proteins that normally exist as monomers, we have developed a method of synthesizing polymers of protein molecules in the solid state. By introducing cysteines at locations where bacteriophage T4 lysozyme molecules contact each other in a crystal and taking advantage of the alignment provided by the lattice, we have obtained polymers of defined polarity up to 25 molecules long that retain enzymatic activity. These polymers then were manipulated mechanically by using a modified scanning force microscope to characterize the force-induced reversible unfolding of the individual lysozyme molecules. This approach should be general and adaptable to many other proteins with known crystal structures. For T4 lysozyme, the force required to unfold the monomers was 64 +/- 16 pN at the pulling speed used. Refolding occurred within 1 sec of relaxation with an efficiency close to 100%. Analysis of the force versus extension curves suggests that the mechanical unfolding transition follows a two-state model. The unfolding forces determined in 1 M guanidine hydrochloride indicate that in these conditions the activation barrier for unfolding is reduced by 2 kcal/mol.

  16. 2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion

    NASA Astrophysics Data System (ADS)

    Kang, Keehoon; Watanabe, Shun; Broch, Katharina; Sepe, Alessandro; Brown, Adam; Nasrallah, Iyad; Nikolka, Mark; Fei, Zhuping; Heeney, Martin; Matsumoto, Daisuke; Marumoto, Kazuhiro; Tanaka, Hisaaki; Kuroda, Shin-Ichi; Sirringhaus, Henning

    2016-08-01

    Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

  17. Highly conductive polymer electrolyte membranes modified with polyethylene glycol-bis-carbamate

    NASA Astrophysics Data System (ADS)

    Fu, Guopeng; Dempsey, Janel; Kyu, Thein

    By virtue of its non-flammability and chemical stability, polyethylene glycol (PEG) networks have shown potential application in all solid-state polymer electrolyte membranes (PEM). However, room temperature ionic conductivity of these PEG based PEMs is inherently low. Plasticization of these PEMs is needed to improve the ionic conductivity. It was demonstrated by this group that small-molecule plasticizers such as succinonitrile, ethylene carbonate, or urea-carbamate can boost ionic conductivity of solid-state polymer electrolyte membranes. Polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction of polyethylene glycol diamine and ethylene carbonate. The PEGBC modified PEM has shown higher ionic conductivity relative to the unmodified PEM. Moreover, PEGBC modified PEM has a better thermal stability relative to ethylene carbonate based liquid electrolyte with enhanced ionic conductivity. Supported by NSF-DMR 1161070, 1502543 and REU 1359321.

  18. Nanostructured all-solid-state supercapacitor based on Li2S-P2S5 glass-ceramic electrolyte

    NASA Astrophysics Data System (ADS)

    Francisco, Brian E.; Jones, Christina M.; Lee, Se-Hee; Stoldt, Conrad R.

    2012-03-01

    While today's lithium-ion batteries offer acceptable energy storage capability, they lack the ability to be cycled repeatedly more than a couple thousand times. Electrochemical capacitors, i.e., supercapacitors, are being developed whose lifetimes exceed 1 × 106 cycles and power densities surpass those of batteries by several times. Here, we present an all-solid-state supercapacitor using a Li2S-P2S5 glass-ceramic electrolyte as both separator and ion conductor. Three device architectures are examined including two with nanostructured electrodes which incorporate multi-walled carbon nanotubes (MWCNTs). Cyclic voltammograms and electrochemical impedance measurements demonstrate that these devices develop reversible double layer capacitance, and a maximum of 7.75 F/g is achieved in the device constructed by mechanically mixing the nanostructured electrodes. Electrochemical impedance spectroscopy explains non-idealities observed when MWCNTs are incorporated in the electrode layers.

  19. Interaction of electrolyte molecules with carbon materials of well-defined porosity: characterization by solid-state NMR spectroscopy.

    PubMed

    Borchardt, Lars; Oschatz, Martin; Paasch, Silvia; Kaskel, Stefan; Brunner, Eike

    2013-09-28

    Electrochemical double-layer capacitors (EDLCs or supercapacitors) are of special potential interest with respect to energy storage. Nearly all EDLCs make use of porous carbons as electrode materials. Further tuning of their performance in EDLC applications requires a better understanding of their properties. In particular, the understanding of the interactions between carbon-based materials and electrolyte solutions is of fundamental interest with respect to future applications. Since the capacitance of carbon-based electrode materials is known to depend on the pore size, we have studied different porous carbon materials of well-defined, variable pore size loaded with 1 M TEABF4 in acetonitrile or with pure acetonitrile using solid-state magic angle spinning (MAS) (1)H, (11)B, and (13)C NMR spectroscopy.

  20. In situ electron holography of electric potentials inside a solid-state electrolyte: Effect of electric-field leakage.

    PubMed

    Aizawa, Yuka; Yamamoto, Kazuo; Sato, Takeshi; Murata, Hidekazu; Yoshida, Ryuji; Fisher, Craig A J; Kato, Takehisa; Iriyama, Yasutoshi; Hirayama, Tsukasa

    2017-07-01

    In situ electron holography is used to observe changes of electric-potential distributions in an amorphous lithium phosphorus oxynitride (LiPON) solid-state electrolyte when different voltages are applied. 2D phase images are simulated by integrating the 3D potential distribution along the electron trajectory through a thin Cu/LiPON/Cu region. Good agreement between experimental and simulated phase distributions is obtained when the influence of the external electric field is taken into account using the 3D boundary-charge method. Based on the precise potential changes, the lithium-ion and lithium-vacancy distributions inside the LiPON layer and electric double layers (EDLs) are inferred. The gradients of the phase drops at the interfaces in relation to EDL widths are discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. A novel small-molecule compound of lithium iodine and 3-hydroxypropionitride as a solid-state electrolyte for lithium–air batteries

    DOE PAGES

    Liu, Fang -Chao; Shadike, Zulipiya; Wang, Xiao -Fang; ...

    2016-06-16

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I–-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium–air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g–1 with a cyclic performance over 10 cycles. Lastly, our findings provide a new way to design solid-state electrolytes toward high-performance lithium–air batteries.

  2. A Novel Small-Molecule Compound of Lithium Iodine and 3-Hydroxypropionitride as a Solid-State Electrolyte for Lithium-Air Batteries.

    PubMed

    Liu, Fang-Chao; Shadike, Zulipiya; Wang, Xiao-Fang; Shi, Si-Qi; Zhou, Yong-Ning; Chen, Guo-Ying; Yang, Xiao-Qing; Weng, Lin-Hong; Zhao, Jing-Tai; Fu, Zheng-Wen

    2016-07-05

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I(-)-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium-air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g(-1) with a cyclic performance over 10 cycles. Our findings provide a new way to design solid-state electrolytes toward high-performance lithium-air batteries.

  3. Solid polymer electrolyte from phosphorylated chitosan

    SciTech Connect

    Fauzi, Iqbal Arcana, I Made

    2014-03-24

    Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the component’s composition respectively on the properties of polymer electrolyte, was carried out by analyzed of it’s characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensile resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 × 10{sup −6} S/cm up to 6.01 × 10{sup −4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 × 10{sup −3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.

  4. Improved Lithium Ionic Conductivity in Composite Polymer Electrolytes with Oxide-Ion Conducting Nanowires.

    PubMed

    Liu, Wei; Lin, Dingchang; Sun, Jie; Zhou, Guangmin; Cui, Yi

    2016-12-27

    Solid Li-ion electrolytes used in all-solid-state lithium-ion batteries (LIBs) are being considered to replace conventional liquid electrolytes that have leakage, flammability, and poor chemical stability issues, which represents one major challenge and opportunity for next-generation high-energy-density batteries. However, the low mobility of lithium ions in solid electrolytes limits their practical applications. Here, we report a solid composite polymer electrolyte with Y2O3-doped ZrO2 (YSZ) nanowires that are enriched with positive-charged oxygen vacancies. The morphologies and ionic conductivities have been studied systemically according to concentration of Y2O3 dopant in the nanowires. In comparison to the conventional filler-free electrolyte with a conductivity of 3.62 × 10(-7) S cm(-1), the composite polymer electrolytes with the YSZ nanowires show much higher ionic conductivity. It indicates that incorporation of 7 mol % of Y2O3-doped ZrO2 nanowires results in the highest ionic conductivity of 1.07 × 10(-5) S cm(-1) at 30 °C. This conductivity enhancement originates from the positive-charged oxygen vacancies on the surfaces of the nanowires that could associate with anions and then release more Li ions. Our work demonstrates a composite polymer electrolyte with oxygen-ion conductive nanowires that could address the challenges of all-solid-state LIBs.

  5. Ionic conduction in polymer composite electrolytes

    NASA Astrophysics Data System (ADS)

    Dam, Tapabrata; Tripathy, Satya N.; Paluch, M.; Jena, S.; Pradhan, D. K.

    2016-05-01

    Conductivity and structural relaxation has been explored from modulus and dielectric loss formalisms respectively for a series of polymer composite electrolytes with zirconia as filler. The temperature dependence of conductivity followed Vogel-Tamman-Fulcher (VTF) behavior, which suggested a close correlation between conductivity and the segmental relaxation process in polymer electrolytes. Vogel temperature (T0) plays significant role in ion conduction process in these kind of materials.

  6. Thin-film solid-state proton NMR measurements using a synthetic mica substrate: Polymer blends

    NASA Astrophysics Data System (ADS)

    VanderHart, David L.; Prabhu, Vivek M.; Lavery, Kristopher A.; Dennis, Cindi L.; Rao, Ashwin B.; Lin, Eric K.

    2009-11-01

    Solid-state proton nuclear magnetic resonance (NMR) measurements are performed successfully on polymer blend thin films through the use of synthetic mica as a substrate. When used as a substrate, synthetic fluorophlogopite mica with its proton-free, diamagnetic character, allows for adequate measurement sensitivity while minimally perturbing the proton thin-film spectra, especially relative to more commonly available natural micas. Specifically, we use multiple-pulse techniques in the presence of magic-angle spinning to measure the degree of mixing in two different polymer blend thin films, polystyrene/poly(xylylene ether) and poly(1-methyladamantyl methacrylate) (PMAdMA)/triphenylsulfonium perfluorobutanesulfonate (TPS-PFBS), spin-coated onto mica substrates. Our earlier studies had focused on bulk systems where NMR signals are stronger, but may not be representative of thin films of the same systems that are relevant to many applications such as photoresist formulations in the electronics industry. The superiority of synthetic over natural paramagnetic mica is demonstrated by the maintenance of resolution and spinning sideband intensities (relative to bulk samples) for the synthetic mica samples. In contrast, degraded resolution and large spinning sidebands are shown to typify spectra of the natural mica samples. This approach can be applied to many other proton measurements of solid thin films, thereby greatly extending the types of systems to be investigated. Magnetic susceptibility measurements are also reported for all micas used.

  7. Thin-film solid-state proton NMR measurements using a synthetic mica substrate: polymer blends.

    PubMed

    VanderHart, David L; Prabhu, Vivek M; Lavery, Kristopher A; Dennis, Cindi L; Rao, Ashwin B; Lin, Eric K

    2009-11-01

    Solid-state proton nuclear magnetic resonance (NMR) measurements are performed successfully on polymer blend thin films through the use of synthetic mica as a substrate. When used as a substrate, synthetic fluorophlogopite mica with its proton-free, diamagnetic character, allows for adequate measurement sensitivity while minimally perturbing the proton thin-film spectra, especially relative to more commonly available natural micas. Specifically, we use multiple-pulse techniques in the presence of magic-angle spinning to measure the degree of mixing in two different polymer blend thin films, polystyrene/poly(xylylene ether) and poly(1-methyladamantyl methacrylate) (PMAdMA)/triphenylsulfonium perfluorobutanesulfonate (TPS-PFBS), spin-coated onto mica substrates. Our earlier studies had focused on bulk systems where NMR signals are stronger, but may not be representative of thin films of the same systems that are relevant to many applications such as photoresist formulations in the electronics industry. The superiority of synthetic over natural paramagnetic mica is demonstrated by the maintenance of resolution and spinning sideband intensities (relative to bulk samples) for the synthetic mica samples. In contrast, degraded resolution and large spinning sidebands are shown to typify spectra of the natural mica samples. This approach can be applied to many other proton measurements of solid thin films, thereby greatly extending the types of systems to be investigated. Magnetic susceptibility measurements are also reported for all micas used.

  8. Comparative analysis of zaleplon complexation with cyclodextrins and hydrophilic polymers in solution and in solid state.

    PubMed

    Jablan, Jasna; Szalontai, Gábor; Jug, Mario

    2012-12-01

    The aim of this work was to investigate the potential synergistic effect of water-soluble polymers (hypromellose, HPMC and polyvinylpyrrolidone, PVP) on zaleplon (ZAL) complexation with parent β-cyclodextrin (βCD) and its randomly methylated derivative (RAMEB) in solution and in solid state. The addition of HPMC to the complexation medium improved ZAL complexation and solubilization with RAMEB (K(ZAL/RAMEB)=156±5M(-1) and K(ZAL/RAMEB/HPMC)=189±8M(-1); p<0.01), while such effect was not observed for βCD (K(ZAL/βCD)=112±2M(-1) and K(ZAL/βCD/HPMC)=119±8M(-1); p>0.05). Although PVP increased the ZAL aqueous solubility from 0.22 to 0.27mg/mL, it did not show any synergistic effects on ZAL solubilization with the cyclodextrins tested. Binary and ternary systems of ZAL with βCD, RAMEB and HPMC were prepared by spray-drying. Differential scanning calorimetry, X-ray powder diffraction and scanning electron microscopy demonstrated a partial ZAL amorphization in spray-dried binary and ternary systems with βCD, while the drug was completely amorphous in all samples with RAMEB. Furthermore, inclusion complex formation in all systems prepared was confirmed by solid-state NMR spectroscopy. The in vitro dissolution rate followed the rank order ZAL/RAMEB/HPMC>ZAL/RAMEB=ZAL/βCD/HPMC>ZAL/βCD≫ZAL, clearly demonstrating the superior performance of RAMEB on ZAL complexation in the solid state and its synergistic effect with HPMC on drug solubility. Surprisingly, when loaded into tablets made with insoluble microcrystalline cellulose, RAMEB complexes had no positive effect on drug dissolution, because HPMC and RAMEB acted as a binders inside the tablets, prolonging their disintegration. Oppositely, the formulation with mannitol, a soluble excipient, containing a ternary RAMEB system, released the complete drug-dose in only 5min, clearly demonstrating its suitability for the development of immediate-release oral formulation of ZAL.

  9. Polymer stability and function for electrolyte and mixed conductor applications

    NASA Astrophysics Data System (ADS)

    Hammond, Paula; Davis, Nicole; Liu, David; Amanchukwu, Chibueze; Lewis, Nate; Shao-Horn, Yang

    2015-03-01

    Polymers exhibit a number of attractive properties as solid state electrolytes for electrochemical energy devices, including the light weight, flexibility, low cost and adaptive transport properties that polymeric materials can exhibit. For a number of applications, mixed ionic and electronic conducting materials are of interest to achieve transport of electrons and holes or ions within an electrode or at the electrode-electrolyte interface (e.g. aqueous batteries, solar water splitting, lithium battery electrode). Using layer-by-layer assembly, a mode of alternating adsorption of charged or complementary hydrogen bonding group, we can design composite thin films that contain bicontinuous networks of electronically and ionically conducting polymers. We have found that manipulation of salt concentration and the use of divalent ions during assembly can significantly enhance the number of free acid anions available for ion hopping. Unfortunately, for certain electrochemical applications, polymer stability is a true challenge. In separate studies, we have been investigating macromolecular systems that may provide acceptable ion transport properties, but withstand the harsh oxidative environment of lithium air systems. An investigation of different polymeric materials commonly examined for electrochemical applications provides insight into polymer design for these kinds of environments. NSF Center for Chemical Innovation, NDSEG Fellowship and Samsung Corporation.

  10. POSS-Based Electrolyte for Efficient Solid-State Dye-Sensitized Solar Cells at Sub-Zero Temperatures.

    PubMed

    Lv, Kai; Zhang, Wei; Zhang, Lu; Wang, Zhong-Sheng

    2016-03-02

    To expand the application of solid-state dye-sensitized solar cells (ssDSSCs) to low temperatures, it is necessary to develop new solid electrolytes with low glass transition temperature (Tg). The Tg is regulated by varying the length of alkyl chain that is connected with the nitrogen atom in the imidazolium ring linked to the polyhedral oligomeric silsesquioxane (POSS). The Tg as low as -8.8 °C is achieved with the POSS grafted with methyl-substituted imidazolium. The effect of alkyl group on the conductivity, Tg, and photovoltaic performance has also been investigated. The conductivity and power conversion efficiency increase with the alkyl length, while the Tg first increases and then decreases with the alkyl length. Among the synthesized POSS-based ionic conductors, the POSS grafted with the methyl-substituted imidazolium yields the highest power conversion efficiency of 6.98% at RT due to its highest conductivity, and the efficiency (6.52%) is still good at -4 °C, as its Tg (-8.8 °C) is lower than the working temperature (-4 °C). This finding suggests that the POSS-based solid electrolyte is promising for subzero-temperature applications of ssDSSCs.

  11. Development of complex hydride-based all-solid-state lithium ion battery applying low melting point electrolyte

    NASA Astrophysics Data System (ADS)

    Suzuki, Shohei; Kawaji, Jun; Yoshida, Koji; Unemoto, Atsushi; Orimo, Shin-ichi

    2017-08-01

    A thermally durable all-solid-state lithium ion battery composed of a complex hydride, oxide electrolytes, and LiNi1/3Mn1/3Co1/3O2 active material is developed. This battery exhibits a discharge capacity of 56 mAh g-1, and the tenth capacity retention ratio is 29% at 150 °C owing to the large contact resistance between the electrolyte layer and the composite positive electrode layer. This large contact resistance is reduced by introducing an adhesive layer comprised of a mixture of LiBH4 and LiNH2 that is easily melted by thermal treatment and fills the voids and pores at the interface between the two layers. As a result, repeated charge-discharge cycles are successfully demonstrated at 150 °C with a high discharge capacity and discharge capacity retention ratio. The first discharge capacity is enhanced to 114 mAh g-1 and the capacity retention ratio at the tenth cycle is improved to 71%. These results demonstrate that using an adhesive layer is an effective measure to reduce the contact resistance and thereby enhance the performance of the battery.

  12. Inorganic-solid-state electrolyte layer deposited by cathodic arc plasma for rapidly switching electrochromic device

    NASA Astrophysics Data System (ADS)

    Chen, Po-Wen; Chang, Chen-Te; Wu, Jin-Yu; Jan, Der-Jun; Li, Yu-Chen; Hsieh, Cheng-Chang; Tsai, Wen-Fa

    2017-08-01

    This work focuses on fabricating a solid electrolyte Ta2O5 thin film deposited by cathodic arc plasm (CAP) deposition through three different ratio of oxygen and argon. In our experiments, refractive index of Ta2O5 films are taken as 2.25, 1.96, 1.9 with various O2/Ar= 1.5, O2/Ar= 2, O2/Ar= 2.4, respectively. Our results show that the refractive index mostly decreased as we increase the oxygen flow rate, in which the minimum is found at 240 sccm. It provides good conduction pathways for ions through smaller thin-film's refractive index that exhibits more porosity voids. This property enhances ion's mobility for electrochromic device causing rapid coloring/bleaching phenomenon. Ta2O5 thin film is suitable as a solid electrolyte layer in center of electrochromic device (ECD) using CAP deposition. As a result, rapid response times were observed in fabricated device with an area of 5 cm×5 cm, exhibiting transmittance optical modulation ΔT = 61.5% (@550 nm) with the bleaching time τ = 8 s and transmittance optical modulation ΔT = 50% (@550 nm) with the coloring time τ = 10 s.

  13. Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

    PubMed Central

    Fu, Kun (Kelvin); Gong, Yunhui; Liu, Boyang; Zhu, Yizhou; Xu, Shaomao; Yao, Yonggang; Luo, Wei; Wang, Chengwei; Lacey, Steven D.; Dai, Jiaqi; Chen, Yanan; Mo, Yifei; Wachsman, Eric; Hu, Liangbing

    2017-01-01

    Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10−3 to 10−4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm2 for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries. PMID:28435874

  14. Polyethylene glycol as a solid polymer electrolyte

    SciTech Connect

    Cha, D.K.; Park, S.M.

    1997-12-01

    Polymer electrolytes were prepared from polyethylene glycol (PEG)-lithium perchlorate complexes and characterized at a stainless steel electrode using a variety of electrochemical techniques. The charge transfer process was affected by the oxide film on the stainless steel electrode surface in the early stages of redox processes. The polymer electrolytes showed a transference number of 0.2 for Li{sup +}. The conductivity of the PEG-10000 electrolyte has been determined to be 4.7 {times} 10{sup {minus}5} S/cm. This rather high value is attributed to the anionic end groups increasing the polarity of the matrix.

  15. Solid-state, polymer-based fiber solar cells with carbon nanotube electrodes.

    PubMed

    Liu, Dianyi; Zhao, Mingyan; Li, Yan; Bian, Zuqiang; Zhang, Luhui; Shang, Yuanyuan; Xia, Xinyuan; Zhang, Sen; Yun, Daqin; Liu, Zhiwei; Cao, Anyuan; Huang, Chunhui

    2012-12-21

    Most previous fiber-shaped solar cells were based on photoelectrochemical systems involving liquid electrolytes, which had issues such as device encapsulation and stability. Here, we deposited classical semiconducting polymer-based bulk heterojunction layers onto stainless steel wires to form primary electrodes and adopted carbon nanotube thin films or densified yarns to replace conventional metal counter electrodes. The polymer-based fiber cells with nanotube film or yarn electrodes showed power conversion efficiencies in the range 1.4% to 2.3%, with stable performance upon rotation and large-angle bending and during long-time storage without further encapsulation. Our fiber solar cells consisting of a polymeric active layer sandwiched between steel and carbon electrodes have potential in the manufacturing of low-cost, liquid-free, and flexible fiber-based photovoltaics.

  16. Synthesis and characterization of alkaline polyvinyl alcohol and poly(epichlorohydrin) blend polymer electrolytes and performance in electrochemical cells

    NASA Astrophysics Data System (ADS)

    Yang, Chun-Chen; Lin, Sheng-Jen; Hsu, Sung-Ting

    Alkaline SPE was obtained from a blend of polyvinyl alcohol (PVA) and poly(epichlorohydrin) (PECH), PVA-PECH, by a solution-cast technique. The PVA host polymer is blended with PECH polymer to provide a polymer electrolyte with improved chemical and mechanical properties. The ionic conductivity of the PVA-PECH polymer electrolytes is between 10 -2 and 10 -3 S cm -1 at room temperature when the blend ratio is varied from 1:0.2 to 1:1. The PVA-PECH polymer was characterized by means of scanning electron microscopy, X-ray diffraction, stress-strain test, cyclic voltammetry, and a.c. impedance spectroscopy. It is found that the polymer electrolytes exhibit good mechanical strength and excellent chemical stability. The electrochemical performance of solid-state Zn-air batteries with various types of the blended polymer electrolyte films is examined by a galvanostatic discharge method.

  17. Chemically robust platform for optical solid-state conducting polymer sensor

    NASA Astrophysics Data System (ADS)

    Holt, A. L.; Bearinger, J. P.; Carter, S. A.

    2006-10-01

    Conjugated polymers are unique materials for use in the development of chemical and biological sensors because of their widely tunable optical and electrical properties that allow them dual functionality as both the sensing element and the signal transducer. Furthermore, as optical photoluminescence based sensors, electroactive polymers are found to exhibit high sensitivity due to the ability of the analyte of interest to quench the photoluminescence of the entire polymer chain. In order to produce a more chemically robust thin film for use as a "solid-state" optical sensor, we succeeded in grafting various poly (3-alkyl-thiophene)s to optically transparent substrates such as glass, quartz, and ITO coated glass. This was accomplished by first grafting a thiophene monomer to the surface then chemically growing the films via oxidative polymerization. XPS studies indicated that each chemical step was accurately understood. The polythiophene growth, unaltered by sonication and tape peeling tests, was uniform across the substrate and could be directed by selective silanization of the substrate. Film thicknesses range from 20 to 200 nm and exhibit varying degrees of surface roughness, depending on the polymerization process. The reaction times and solvents were varied in order to optimize the desired film properties. The absorption and photoluminescence properties of the thin films compared well with literature on spun-cast polythiophene films, as did the electrical conductivities of the doped and undoped material. The photoluminescence intensities of the films are found to be unaffected by paraquat in water but are sensitive to trace amounts of ferric chloride in acetonitrile with measurable Stern Volmer constants.

  18. Passivation-free solid state battery

    DOEpatents

    Abraham, Kuzhikalail M.; Peramunage, Dharmasena

    1998-01-01

    This invention pertains to passivation-free solid-state rechargeable batteries composed of Li.sub.4 Ti.sub.5 O.sub.12 anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn.sub.2 O.sub.4, LiCoO.sub.2, LiNiO.sub.2 and LiV.sub.2 O.sub.5 and their derivatives.

  19. Passivation-free solid state battery

    DOEpatents

    Abraham, K.M.; Peramunage, D.

    1998-06-16

    This invention pertains to passivation-free solid-state rechargeable batteries composed of Li{sub 4}Ti{sub 5}O{sub 12} anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn{sub 2}O{sub 4}, LiCoO{sub 2}, LiNiO{sub 2} and LiV{sub 2}O{sub 5} and their derivatives. 5 figs.

  20. Fuel cell electrolyte membrane with basic polymer

    DOEpatents

    Larson, James M.; Pham, Phat T.; Frey, Matthew H.; Hamrock, Steven J.; Haugen, Gregory M.; Lamanna, William M.

    2012-12-04

    The present invention is an electrolyte membrane comprising an acid and a basic polymer, where the acid is a low-volatile acid that is fluorinated and is either oligomeric or non-polymeric, and where the basic polymer is protonated by the acid and is stable to hydrolysis.

  1. Fuel cell electrolyte membrane with basic polymer

    DOEpatents

    Larson, James M.; Pham, Phat T.; Frey, Matthew H.; Hamrock, Steven J.; Haugen, Gregory M.; Lamanna, William M.

    2010-11-23

    The present invention is an electrolyte membrane comprising an acid and a basic polymer, where the acid is a low-volatile acid that is fluorinated and is either oligomeric or non-polymeric, and where the basic polymer is protonated by the acid and is stable to hydrolysis.

  2. Ionic Liquid-Based Polymer Electrolytes via Surfactant-Assisted Polymerization at the Plasma-Liquid Interface.

    PubMed

    Tran, Quoc Chinh; Bui, Van-Tien; Dao, Van-Duong; Lee, Joong-Kee; Choi, Ho-Suk

    2016-06-29

    We first report an innovative method, which we refer to as interfacial liquid plasma polymerization, to chemically cross-link ionic liquids (ILs). By this method, a series of all-solid state, free-standing polymer electrolytes is successfully fabricated where ILs are used as building blocks and ethylene oxide-based surfactants are employed as an assisted-cross-linking agent. The thickness of the films is controlled by the plasma exposure time or the ratio of surfactant to ILs. The chemical structure and properties of the polymer electrolyte are characterized by scanning electron microscopy (SEM), Fourier transformation infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and electrochemical impedance spectroscopy (EIS). Importantly, the underlying polymerization mechanism of the cross-linked IL-based polymer electrolyte is studied to show that fluoroborate or halide anions of ILs together with the aid of a small amount of surfactants having ethylene oxide groups are necessary to form cross-linked network structures of the polymer electrolyte. The ionic conductivity of the obtained polymer electrolyte is 2.28 × 10(-3) S·cm(-1), which is a relatively high value for solid polymer electrolytes synthesized at room temperature. This study can serve as a cornerstone for developing all-solid state polymer electrolytes with promising properties for next-generation electrochemical devices.

  3. In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

    PubMed Central

    Johnson, Grant E.; Wang, Bingbing; Laskin, Julia

    2016-01-01

    Molecular-level understanding of electrochemical processes occurring at electrode–electrolyte interfaces (EEIs) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and application of solid-state in situ thin-film electrochemical cells to explore redox and catalytic processes occurring at well-defined EEIs generated using soft-landing (SL) of mass- and charge-selected cluster ions. In situ cells with excellent mass-transfer properties are fabricated using carefully designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, demonstrated to be a unique tool for studying fundamental processes occurring at EEIs. Using an aprotic cell, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEIs with POM anions generated by electrospray ionization and gas-phase dissociation. Additionally, a proton-conducting cell has been developed to characterize the oxygen reduction activity of bare Pt clusters (Pt30 ∼1 nm diameter), thus demonstrating the capability of the cell for probing catalytic reactions in controlled gaseous environments. By combining the developed in situ electrochemical cell with ion SL we established a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely defined conditions. This capability will advance the molecular-level understanding of processes occurring at EEIs that are critical to many energy-related technologies. PMID:27821731

  4. In situ solid-state electrochemistry of mass-selected ions at well-defined electrode-electrolyte interfaces.

    PubMed

    Prabhakaran, Venkateshkumar; Johnson, Grant E; Wang, Bingbing; Laskin, Julia

    2016-11-22

    Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEIs) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and application of solid-state in situ thin-film electrochemical cells to explore redox and catalytic processes occurring at well-defined EEIs generated using soft-landing (SL) of mass- and charge-selected cluster ions. In situ cells with excellent mass-transfer properties are fabricated using carefully designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, demonstrated to be a unique tool for studying fundamental processes occurring at EEIs. Using an aprotic cell, the effect of charge state ([Formula: see text]) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEIs with POM anions generated by electrospray ionization and gas-phase dissociation. Additionally, a proton-conducting cell has been developed to characterize the oxygen reduction activity of bare Pt clusters (Pt30 ∼1 nm diameter), thus demonstrating the capability of the cell for probing catalytic reactions in controlled gaseous environments. By combining the developed in situ electrochemical cell with ion SL we established a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely defined conditions. This capability will advance the molecular-level understanding of processes occurring at EEIs that are critical to many energy-related technologies.

  5. In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

    SciTech Connect

    Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing; Laskin, Julia

    2016-11-07

    Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.

  6. Solid State Electrochromic Display Device

    NASA Astrophysics Data System (ADS)

    Bohnke, Odile; Bohnke, Claude

    1989-12-01

    Polymer electrolyte - based display devices are of growing importance in view of their specific properties compared to liquid devices. One of them is, of course, the possibility to obtain all solid-state devices without leakage and another one, may be more interesting, is the possibility to obtain a strong dependence of the response time of the display on the temperature. Such a property may be conveniently used for the realization of devices with specific applications such as thermal sensors or heated display devices, for instance. The optical response characteristics of amorphous W03/polymeric electrolyte/stainless steel electrochromic display (ECD) devices have been investigated using cyclic voltammetry and chronoamperometry coupled with optical reflection measurements. The variations of both the colouration time and the colouring efficency with temperature are related to both the ionic conductivity of the polymer and the phase diagram of the polymer.

  7. Nanopore gating with an anchored polymer in a switching electrolyte bias

    NASA Astrophysics Data System (ADS)

    Wells, Craig C.; Jou, Ining A.; Melnikov, Dmitriy V.; Gracheva, Maria E.

    2016-03-01

    In this work, we theoretically study the interaction between a solid state membrane equipped with a nanopore and a tethered, negatively charged polymer chain subjected to a time-dependent applied electrolyte bias. In order to describe the movement of the chain in the biomolecule-membrane system immersed in an electrolyte solution, Brownian dynamics is used. We show that we can control the polymer's equilibrium position with various applied electrolyte biases: for a sufficiently positive bias, the chain extends inside the pore, and the removal of the bias causes the polymer to leave the pore. Corresponding to a driven process, we find that the time it takes for a biomolecular chain to enter and extend into a nanopore in a positive bias almost increases linearly with chain length while the amount of time it takes for a polymer chain to escape the nanopore is mainly governed by diffusion.

  8. Nanopore gating with an anchored polymer in a switching electrolyte bias

    NASA Astrophysics Data System (ADS)

    Wells, Craig; Jou, Ining; Melnikov, Dmitriy; Gracheva, Maria

    We theoretically study the interaction between a tethered, negatively charged polymer chain of varying lengths and a solid state membrane with a nanopore when subject to a time-dependent applied electrolyte bias. Brownian dynamics is used to describe the movement of a biomolecule interacting with a membrane immersed in an electrolyte solution. With the help of an applied electrolyte bias, we can control polymer's equilibrium position, extending it inside the pore for a sufficiently positive bias. We find that the amount of time a polymer takes to enter and extend inside a nanopore in a positive bias increases nearly linearly with the chain length, corresponding to an electrically driven process. The time it takes for the chain to exit the pore, however, increases nearly quadratically with chain length, corresponding to a diffusion process. Understanding the dynamical behavior of the tethered polymer chain will facilitate further advances in this area of nanotechnology. NSF DMR and CBET Grant No. 1352218.

  9. Ionic Liquid-Enhanced Solid State Electrolyte Interface (SEI) for Lithium Sulfur Batteries

    SciTech Connect

    Zheng, Jianming; Gu, Meng; Chen, Honghao; Meduri, Praveen; Engelhard, Mark H.; Zhang, Jiguang; Liu, Jun; Xiao, Jie

    2013-05-16

    Li-S battery is a complicated system with many challenges existing before its final market penetration. While most of the reported work for Li-S batteries is focused on the cathode design, we demonstrate in this work that the anode consumption accelerated by corrosive polysulfide solution also critically determines the Li-S cell performance. To validate this hypothesis, ionic liquid (IL) N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Py14TFSI) has been employed to modify the properties of SEI layer formed on Li metal surface in Li-S batteries. It is found that the IL-enhanced passivation film on the lithium anode surface exhibits much different morphology and chemical compositions, effectively protecting lithium metal from continuous attack by soluble polysulfides. Therefore, both cell impedance and the irreversible consumption of polysulfides on lithium metal are reduced. As a result, the Coulombic efficiency and the cycling stability of Li-S batteries have been greatly improved. After 120 cycles, Li-S battery cycled in the electrolyte containing IL demonstrates a high capacity retention of 94.3% at 0.1 C rate. These results unveil another important failure mechanism for Li-S batteries and shin the light on the new approaches to improve Li-S battery performances.

  10. Bendable and thin sulfide solid electrolyte film: a new electrolyte opportunity for free-standing and stackable high-energy all-solid-state lithium-ion batteries.

    PubMed

    Nam, Young Jin; Cho, Sung-Ju; Oh, Dae Yang; Lim, Jun-Muk; Kim, Sung Youb; Song, Jun Ho; Lee, Young-Gi; Lee, Sang-Young; Jung, Yoon Seok

    2015-05-13

    Bulk-type all-solid-state lithium batteries (ASLBs) are considered a promising candidate to outperform the conventional lithium-ion batteries. Unfortunately, the current technology level of ASLBs is in a stage of infancy in terms of cell-based (not electrode-material-based) energy densities and scalable fabrication. Here, we report on the first ever bendable and thin sulfide solid electrolyte films reinforced with a mechanically compliant poly(paraphenylene terephthalamide) nonwoven (NW) scaffold, which enables the fabrication of free-standing and stackable ASLBs with high energy density and high rate capabilities. The ASLB, using a thin (∼70 μm) NW-reinforced SE film, exhibits a 3-fold increase of the cell-energy-density compared to that of a conventional cell without the NW scaffold.

  11. Enzymatic logic calculation systems based on solid-state electrochemiluminescence and molecularly imprinted polymer film electrodes.

    PubMed

    Lian, Wenjing; Liang, Jiying; Shen, Li; Jin, Yue; Liu, Hongyun

    2017-09-18

    The molecularly imprinted polymer (MIP) films were electropolymerized on the surface of Au electrodes with luminol and pyrrole (PY) as the two monomers and ampicillin (AM) as the template molecule. The electrochemiluminescence (ECL) intensity peak of polyluminol (PL) of the AM-free MIP films at 0.7V vs Ag/AgCl could be greatly enhanced by AM rebinding. In addition, the ECL signals of the MIP films could also be enhanced by the addition of glucose oxidase (GOD)/glucose and/or ferrocenedicarboxylic acid (Fc(COOH)2) in the testing solution. Moreover, Fc(COOH)2 exhibited cyclic voltammetric (CV) response at the AM-free MIP film electrodes. Based on these results, a binary 3-input/6-output biomolecular logic gate system was established with AM, GOD and Fc(COOH)2 as inputs and the ECL responses at different levels and CV signal as outputs. Some functional non-Boolean logic devices such as an encoder, a decoder and a demultiplexer were also constructed on the same platform. Particularly, on the basis of the same system, a ternary AND logic gate was established. The present work combined MIP film electrodes, the solid-state ECL, and the enzymatic reaction together, and various types of biomolecular logic circuits and devices were developed, which opened a novel avenue to construct more complicated bio-logic gate systems. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Improving pore filling of gel electrolyte and charge transport in photoanode for high-efficiency quasi-solid-state dye-sensitized solar cells.

    PubMed

    Wang, Baohua; Chang, Shuai; Lee, Lawrence Tien Lin; Zheng, Shizhao; Wong, King Yong; Li, Quan; Xiao, Xudong; Chen, Tao

    2013-09-11

    We demonstrate the enhancement of pore-filling and wettability of gel electrolyte in quasi-solid-state dye-sensitized solar cells (DSSCs) by developing a kinetically driven electrolyte infiltration approach, in which the air purging provides the driving force. This method renders fast electrolyte diffusion throughout the three-dimensional TiO2 nanoparticle network, promising for large-area device fabrication. In addition, for the first time we incorporate multiwalled carbon nanotubes into the anode of quasi-solid-state DSSCs to improve the charge transfer efficiency and fill factor. These advancements finally generate an efficiency exceeding 7.0%, much higher than the device efficiency of 5.5% fabricated by the conventional method.

  13. Pseudo-binary electrolyte, LiBH4-LiCl, for bulk-type all-solid-state lithium-sulfur battery

    NASA Astrophysics Data System (ADS)

    Unemoto, Atsushi; Chen, ChunLin; Wang, Zhongchang; Matsuo, Motoaki; Ikeshoji, Tamio; Orimo, Shin-ichi

    2015-06-01

    The ionic conduction and electrochemical and thermal stabilities of the LiBH4-LiCl solid-state electrolyte were investigated for use in bulk-type all-solid-state lithium-sulfur batteries. The LiBH4-LiCl solid-state electrolyte exhibiting a lithium ionic conductivity of log ≤ft( σ /S c{{m}-1} \\right)=-3.3 at 373 K, forms a reversible interface with a lithium metal electrode and has a wide electrochemical potential window up to 5 V. By means of the high-energy mechanical ball-milling technique, we prepared a composite powder consisting of elemental sulfur and mixed conductive additive, i.e., Ketjen black and Maxsorb. In that composite powder, homogeneous dispersion of the materials is achieved on a nanometer scale, and thereby a high concentration of the interface among them is induced. Such nanometer-scale dispersals of both elemental sulfur and carbon materials play an important role in enhancing the electrochemical reaction of elemental sulfur. The highly deformable LiBH4-LiCl electrolyte assists in the formation of a high concentration of tight interfaces with the sulfur-carbon composite powder. The LiBH4-LiCl electrolyte also allows the formation of the interface between the positive electrode and the electrolyte layers, and thus the Li-ion transport paths are established at that interface. As a result, our battery exhibits high discharge capacities of 1377, 856, and 636 mAh g-1 for the 1st, 2nd, and 5th discharges, respectively, at 373 K. These results imply that complex hydride-based solid-state electrolytes that contain Cl-ions in the crystal would be integrated into rechargeable batteries.

  14. Pseudo-binary electrolyte, LiBH4-LiCl, for bulk-type all-solid-state lithium-sulfur battery.

    PubMed

    Unemoto, Atsushi; Chen, ChunLin; Wang, Zhongchang; Matsuo, Motoaki; Ikeshoji, Tamio; Orimo, Shin-Ichi

    2015-01-26

    The ionic conduction and electrochemical and thermal stabilities of the LiBH4-LiCl solid-state electrolyte were investigated for use in bulk-type all-solid-state lithium-sulfur batteries. The LiBH4-LiCl solid-state electrolyte exhibiting a lithium ionic conductivity of [Formula: see text] at 373 K, forms a reversible interface with a lithium metal electrode and has a wide electrochemical potential window up to 5 V. By means of the high-energy mechanical ball-milling technique, we prepared a composite powder consisting of elemental sulfur and mixed conductive additive, i.e., Ketjen black and Maxsorb. In that composite powder, homogeneous dispersion of the materials is achieved on a nanometer scale, and thereby a high concentration of the interface among them is induced. Such nanometer-scale dispersals of both elemental sulfur and carbon materials play an important role in enhancing the electrochemical reaction of elemental sulfur. The highly deformable LiBH4-LiCl electrolyte assists in the formation of a high concentration of tight interfaces with the sulfur-carbon composite powder. The LiBH4-LiCl electrolyte also allows the formation of the interface between the positive electrode and the electrolyte layers, and thus the Li-ion transport paths are established at that interface. As a result, our battery exhibits high discharge capacities of 1377, 856, and 636 mAh g(-1) for the 1st, 2nd, and 5th discharges, respectively, at 373 K. These results imply that complex hydride-based solid-state electrolytes that contain Cl-ions in the crystal would be integrated into rechargeable batteries.

  15. Improved performance of Li hybrid solid polymer electrolyte cells

    NASA Astrophysics Data System (ADS)

    Nagasubramanian, G.; Bronstein, Lyudmila; Carini, John

    The seminal research by Wright et al. on polyethylene oxide (PEO) solid polymer electrolyte (SPE) generated intense interest in all solid-state rechargeable lithium batteries. Following this a number of researchers have studied the physical, electrical and transport properties of thin film PEO electrolyte containing Li salt. These studies have clearly identified the limitations of the PEO electrolyte. Chief among the limitations are a low cation transport number (t +), high crystallinity and segmental motion of the polymer chain, which carries the cation through the bulk electrolyte. While low t + leads to cell polarization and increase in cell resistance high T g reduces conductivity at and around room temperatures. For example, the conductivity of PEO electrolyte containing lithium salt is <10 -7 S cm -1 at room temperature. Although modified PEO electrolytes with lower T g exhibited higher conductivity (∼10 -5 S cm -1 at RT) the t + is still very low ∼0.25 for lithium ion. Numerous other attempts to improving t + have met with limited success. The latest approach involves integrating nano domains of inorganic moieties, such as silcate, alumosilicate, etc. within the polymer component. This approach yields an inorganic-organic component (OIC) based polymer electrolyte with higher conductivity and t + for Li + . This paper describes the improved electrical and electrochemical properties of OIC-based polymer electrolyte and cells containing Li anode with either a TiS 2 cathode or Mag-10 carbon electrode. Several solid polymer electrolytes derived from silicate OIC and salt-in-polymer constituent based on Li triflate (LiTf) and PEO are studied. A typical composition of the SPE investigated in this work consists of 600 kDa PEO, lithium triflate (LiTf, LiSO 3CF 3) and 55% of silicate based on (3-glycidoxypropyl)trimethoxysilane and tetramethoxysilane at molar ratio 4:1 and 0.65 mol% of aluminum(tri- sec-butoxide) (GTMOS-Al1-900k-55%). Several pouch cells

  16. Low Temperature Synthesis of Cubic-phase Fast-ionic Conducting Bi-doped Garnet Solid State Electrolytes

    NASA Astrophysics Data System (ADS)

    Schwanz, Derek K.; Marinero, Ernesto

    We report on the synthesis of cubic-phase fast ionic conducting garnet solid state electrolytes based on LiLaZrO (LLZO) at unprecedented low synthesis temperatures. Ionic conductivities around 1.2 x 10-4 S/cm are readily achieved. Bismuth aliovalent substitution into LLZO utilizing the Pechini processing method is successfully employed to synthesize LiLaZrBiO compounds. Cubic phase LiLaZrBiO powders are generated in the temperature range 650C to 900C in air. In contrast, in the absence of Bi and under identical synthesis conditions, the cubic phase of LiLaZrO is not formed below 750C and a transformation to the poor ionically conducting tetragonal phase is observed at 800C for the undoped compound. The critical role of Bi in lowering the formation temperature of the garnet cubic phase and the improvements in ionic conductivity are elucidated in this work through microstructural and electrochemical studies.

  17. Performance enhancement of dye-sensitized solar cells using an ester-functionalized imidazolium iodide as the solid state electrolyte.

    PubMed

    Xu, Xin; Wang, Hong; Gong, Feng; Zhou, Gang; Wang, Zhong-Sheng

    2013-04-24

    Linking an ester group to the imidazolium ring has been demonstrated to improve solar cell performance in terms of short-circuit photocurrent (Jsc), open-circuit photovoltage (Voc), and fill factor (FF) in particular, when the imidazolium iodide mixed with iodine and LiI is used as a solid state electrolyte of dye-sensitized solar cells. Herein, the effect of ester group on solar cell performance has been investigated by means of intensity modulated photocurrent/photovoltage and electrochemical impedance spectroscopy. From the alkyl- to ester-functionalized imidazolium iodide, the increase in Jsc is attributed to the increased charge collection efficiency due to the enhanced conductivity, the increase in Voc is caused by the upward shift of conduction band edge of TiO2, which compensates for the voltage loss arising from the higher charge recombination rate, and the remarkable increase in FF is attributed to the decreased series resistance along with the increased Voc and decreased diode quality factor.

  18. Fast lithium-ion conducting thin-film electrolytes integrated directly on flexible substrates for high-power solid-state batteries.

    PubMed

    Ihlefeld, Jon F; Clem, Paul G; Doyle, Barney L; Kotula, Paul G; Fenton, Kyle R; Apblett, Christopher A

    2011-12-15

    By utilizing an equilibrium processing strategy that enables co-firing of oxides and base metals, a means to integrate the lithium-stable fast lithium-ion conductor lanthanum lithium tantalate directly with a thin copper foil current collector appropriate for a solid-state battery is presented. This resulting thin-film electrolyte possesses a room temperature lithium-ion conductivity of 1.5 × 10(-5) S cm(-1) , which has the potential to increase the power of a solid-state battery over current state of the art.

  19. Electrodeposited polyethylenedioxythiophene with infiltrated gel electrolyte interface: a close contest of an all-solid-state supercapacitor with its liquid-state counterpart

    NASA Astrophysics Data System (ADS)

    Anothumakkool, Bihag; Torris A. T, Arun; Bhange, Siddheshwar N.; Badiger, Manohar V.; Kurungot, Sreekumar

    2014-05-01

    We report the design of an all-solid-state supercapacitor, which has charge storage characteristics closely matching that of its liquid-state counterpart even under extreme temperature and humidity conditions. The prototype is made by electro-depositing polyethylenedioxythiophene (PEDOT) onto the individual carbon fibers of a porous carbon substrate followed by intercalating the matrix with polyvinyl alcohol-sulphuric acid (PVA-H2SO4) gel electrolyte. The electrodeposited layer of PEDOT maintained a flower-like growth pattern along the threads of each carbon fiber. This morphology and the alignment of PEDOT led to an enhanced surface area and electrical conductivity, and the pores in the system enabled effective intercalation of the polymer-gel electrolyte. Thus, the established electrode-electrolyte interface nearly mimics that of its counterpart based on the liquid electrolyte. Consequently, the solid device attained very low internal resistance (1.1 Ω cm-2) and a high specific capacitance (181 F g-1) for PEDOT at a discharge current density of 0.5 A g-1. Even with a high areal capacitance of 836 mF cm-2 and volumetric capacitance of 28 F cm-3, the solid device retained a mass-specific capacitance of 111 F g-1 for PEDOT. This is in close agreement with the value displayed by the corresponding liquid-state system (112 F g-1), which was fabricated by replacing the gel electrolyte with 0.5 M H2SO4. The device also showed excellent charge-discharge stability for 12 000 cycles at 5 A g-1. The performance of the device was consistent even under wide-ranging humidity (30-80%) and temperature (-10 to 80 °C) conditions. Finally, a device fabricated by increasing the electrode area four times was used to light an LED, which validated the scalability of the process.We report the design of an all-solid-state supercapacitor, which has charge storage characteristics closely matching that of its liquid-state counterpart even under extreme temperature and humidity conditions

  20. New lithium metal polymer solid state battery for an ultrahigh energy: nano C-LiFePO₄ versus nano Li1.2V₃O₈.

    PubMed

    Hovington, P; Lagacé, M; Guerfi, A; Bouchard, P; Mauger, A; Julien, C M; Armand, M; Zaghib, K

    2015-04-08

    Novel lithium metal polymer solid state batteries with nano C-LiFePO4 and nano Li1.2V3O8 counter-electrodes (average particle size 200 nm) were studied for the first time by in situ SEM and impedance during cycling. The kinetics of Li-motion during cycling is analyzed self-consistently together with the electrochemical properties. We show that the cycling life of the nano Li1.2V3O8 is limited by the dissolution of the vanadium in the electrolyte, which explains the choice of nano C-LiFePO4 (1300 cycles at 100% DOD): with this olivine, no dissolution is observed. In combination with lithium metal, at high loading and with a stable SEI an ultrahigh energy density battery was thus newly developed in our laboratory.

  1. Ionic liquids in a poly ethylene oxide cross-linked gel polymer as an electrolyte for electrical double layer capacitor

    NASA Astrophysics Data System (ADS)

    Chaudoy, V.; Tran Van, F.; Deschamps, M.; Ghamouss, F.

    2017-02-01

    In the present work, we developed a gel polymer electrolyte via the incorporation of a room temperature ionic liquid into a cross-linked polymer matrix. The cross-linked gel electrolyte was prepared using a free radical polymerization of methacrylate and dimethacrylate oligomers dissolved in 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide. Combining the advantages of the ionic liquids and of conventional polymers, the cross-linked gel polymer electrolyte was used both as a separator and as an electrolyte for a leakage-free and non-flammable EDLC supercapacitor. The quasi-all solid-state supercapacitors showed rather good capacitance, power and energy densities by comparison to a liquid electrolyte-based EDLC.

  2. Composite Polymer Electrolytes Based on Hyperbranched Polymer and Application to Lithium Polymer Batteries

    NASA Astrophysics Data System (ADS)

    Itoh, Takahito; Ichikawa, Yosiaki; Miyamura, Yuko; Uno, Takahiro; Kubo, Masataka; Takeda, Yasuo; Li, Qi; Yamamoto, Osamu

    2002-12-01

    Composite polymer electrolytes based on poly(ethylene oxide) (PEO), hyperbranched polymer (HBP), poly[bis(triethylene glycol)benzoate] capped with an acetyl group, a ceramic filler BaTiO3, and a lithium salt such as LiN(CF3SO2)2, LiN(CF3CF2SO2)2, or LiN(CF3SO2)2/LiPF6 were investigated as the electrolyte for all solid-state lithium polymer batteries. The ionic conductivities of the optimized [(PEO-20wt%HBP)12(LiN(CF3SO2)2)]-10wt% BaTiO3, [(PEO-20wt%HBP)12(LiN(CF3CF2SO2)2)]-10wt%BaTiO3, and [(PEO-10wt%HBP)10(LiN(CF3SO2)2-10wt%LiPF6)]-10wt%BaTiO3 electrolytes were found to be 2.6 × 10-4 S/cm at 30 °C and 5.2 × 10-3 S/cm at 80 °C, 1.3 × 10-4 S/cm at 30 °C and 1.6 × 10-3 S/cm at 80 °C, and 1.6 × 10-4 S/cm at 25 °C and 1.5 × 10-3 S/cm at 60 °C, respectively. The lithium polymer batteries composed of the [(PEO-10wt%HBP)10(LiN(CF3SO2)2-10wt%LiPF6)]-10wt%BaTiO3 electrolyte and 4 V class cathode, LiNi0.8Co0.2O2, showed excellent charge-discharge cycling performance. The initial cathode discharge capacity of 154 mAh/g declined only 0.1 %/cycle during first 30 cycles at 60 °C.

  3. Solid-State Li-Ion Batteries Using Fast, Stable, Glassy Nanocomposite Electrolytes for Good Safety and Long Cycle-Life.

    PubMed

    Tan, Guoqiang; Wu, Feng; Zhan, Chun; Wang, Jing; Mu, Daobin; Lu, Jun; Amine, Khalil

    2016-03-09

    The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li(+)-conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO2, LiNi1/3Co1/3Mn1/3O2, or LiFePO4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparent glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational engineering of advanced Li-ion batteries and other electrochemical devices.

  4. Solid-State Li-Ion Batteries Using Fast, Stable, Glassy Nanocomposite Electrolytes for Good Safety and Long Cycle-Life

    SciTech Connect

    Tan, Guoqiang; Wu, Feng; Zhan, Chun; Wang, Jing; Mu, Daobin; Lu, Jun; Amine, Khalil

    2016-03-09

    The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li+ conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO2, LiNi1/3Co1/3Mn1/3O2, or LiFePO4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparent glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational engineering of advanced Li-ion batteries and other electrochemical devices.

  5. All-solid-state electrochemical capacitors using MnO2 electrode/SiO2-Nafion electrolyte composite prepared by the sol-gel process

    NASA Astrophysics Data System (ADS)

    Shimamoto, Kazushi; Tadanaga, Kiyoharu; Tatsumisago, Masahiro

    2014-02-01

    Electrode-electrolyte composites of MnO2 active material, acetylene black (AB), and SiO2-Nafion solid electrolyte were prepared using the sol-gel process to form good solid-solid interfaces. The composites were obtained by the addition of MnO2 and AB into a sol of hydrolyzed tetraethoxysilane with Nafion, and successive solidification of the precursor sol. Scanning electron microscope and energy dispersive X-ray spectroscopy measurements show that good solid-solid interface is formed between electrodes and solid electrolytes in the composites. All-solid-state hybrid capacitors were fabricated using the composites or the hand-grinding mixture of MnO2, AB and SiO2-Nafion powder as positive electrodes, activated carbon powder as a negative electrode, and phosphosilicate gel as a solid electrolyte. The all-solid-state hybrid capacitors using the composites exhibit larger capacitances and better rate performance than the capacitors using the electrode prepared by hand-mixing of powders. Specific discharge capacitances of the capacitor with the composite are 85 F g-1 for the one with the composite electrode and 48 F g-1 for the one with the hand-mixed electrode, at 1 mA cm-2. Moreover, the all-solid-state capacitors using the composite electrode can be operated at temperatures between -30 °C and 60 °C.

  6. Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

    SciTech Connect

    Black, Hayden T.; Harrison, Katharine Lee

    2016-10-01

    The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Li+ ions, and that the mobility of polymer associated Li+ was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li+ within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.

  7. Single-Ion Block Copoly(ionic liquid)s as Electrolytes for All-Solid State Lithium Batteries.

    PubMed

    Porcarelli, Luca; Shaplov, Alexander S; Salsamendi, Maitane; Nair, Jijeesh R; Vygodskii, Yakov S; Mecerreyes, David; Gerbaldi, Claudio

    2016-04-27

    Polymer electrolytes have been proposed as replacement for conventional liquid electrolytes in lithium-ion batteries (LIBs) due to their intrinsic enhanced safety. Nevertheless, the power delivery of these materials is limited by the concentration gradient of the lithium salt. Single-ion conducting polyelectrolytes represent the ideal solution since their nature prevents polarization phenomena. Herein, the preparation of a new family of single-ion conducting block copolymer polyelectrolytes via reversible addition-fragmentation chain transfer polymerization technique is reported. These copolymers comprise poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) and poly(ethylene glycol) methyl ether methacrylate blocks. The obtained polyelectrolytes show low Tg values in the range of -61 to 0.6 °C, comparatively high ionic conductivity (up to 2.3 × 10(-6) and 1.2 × 10(-5) S cm(-1) at 25 and 55 °C, respectively), wide electrochemical stability (up to 4.5 V versus Li(+)/Li), and a lithium-ion transference number close to unity (0.83). Owing to the combination of all mentioned properties, the prepared polymer materials were used as solid polyelectrolytes and as binders in the elaboration of lithium-metal battery prototypes with high charge/discharge efficiency and excellent specific capacity (up to 130 mAh g(-1)) at C/15 rate.

  8. Characterization of Sputter-Deposited LiCoO2 Thin Film Grown on NASICON-type Electrolyte for Application in All-Solid-State Rechargeable Lithium Battery.

    PubMed

    Kim, Hee-Soo; Oh, Yoong; Kang, Ki Hoon; Kim, Ju Hwan; Kim, Joosun; Yoon, Chong Seung

    2017-05-17

    All-solid-state Li-rechargeable batteries using a 500 nm-thick LiCoO2 (LCO) film deposited on two NASICON-type solid electrolyte substrates, LICGC (OHARA Inc.) and Li1.3Al0.3Ti1.7(PO4)3 (LATP), are constructed. The postdeposition annealing temperature prior to the cell assembly is critical to produce a stable sharp LCO/electrolyte interface and to develop a strong crystallographic texture in the LCO film, conducive to migration of Li ions. Although the cells deliver a limited discharge capacity, the cells cycled stably for 50 cycles. The analysis of the LCO/electrolyte interfaces after cycling demonstrates that the sharp interface, once formed by proper thermal annealing, will remain stable without any evidence for contamination and with minimal intermixing of the constituent elements during cycling. Hence, although ionic conductivity of the NASICON-type solid electrolyte is lower than that of the sulfide electrolytes, the NACSICON-type electrolytes will maintain a stable interface in contact with a LCO cathode, which should be beneficial to improving the capacity retention as well as the rate capability of the all-solid state cell.

  9. Electrospinning of an Alkaline Polymer Electrolyte

    NASA Astrophysics Data System (ADS)

    Roddecha, Supacharee; Dong, Zexuan; Wu, Yiquan; Anthamatten, Mitchell

    2010-03-01

    The polymer electrolyte membrane is a key component of the low temperature fuel cell to block fuel and electron crossover, while enabling ions to pass and complete the half-cell reactions. Proton exchange membranes (PEMs) are anion-containing polymers, such as Nafion, which offer proton conduction pathways. Alkaline polymer electrolytes utilize hydroxyl anions as charge carriers and are currently being researched as an alternative to PEMs because they may offer the use of inexpensive metal catalysts. However, hydroxyl anion in an alkaline electrolyte has relatively low mobility compared to that of protons in an acid electrolyte; hence a high concentration of OH^- is required to obtain high ionic conductivity. Here, we report the use of an electrospinning process to prepare nonwoven membranes. Polysulfones are first functionalized with varied ionic content of quaternary ammonium functional groups and then are electrospun to get alkaline electrolyte mat. The morphology at various ionic content, mechanical property, and in-plane conductivity of resulting films will be discussed and compared to solvent-cast films of the same material.

  10. A novel small-molecule compound of lithium iodine and 3-hydroxypropionitride as a solid-state electrolyte for lithium–air batteries

    SciTech Connect

    Liu, Fang -Chao; Shadike, Zulipiya; Wang, Xiao -Fang; Shi, Si -Qi; Zhou, Yong -Ning; Chen, Guo -Ying; Yang, Xiao -Qing; Weng, Lin -Hong; Zhao, Jing -Tai; Fu, Zheng -Wen

    2016-06-16

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I–-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium–air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g–1 with a cyclic performance over 10 cycles. Lastly, our findings provide a new way to design solid-state electrolytes toward high-performance lithium–air batteries.

  11. A novel small-molecule compound of lithium iodine and 3-hydroxypropionitride as a solid-state electrolyte for lithium–air batteries

    SciTech Connect

    Liu, Fang -Chao; Shadike, Zulipiya; Wang, Xiao -Fang; Shi, Si -Qi; Zhou, Yong -Ning; Chen, Guo -Ying; Yang, Xiao -Qing; Weng, Lin -Hong; Zhao, Jing -Tai; Fu, Zheng -Wen

    2016-06-16

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I–-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium–air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g–1 with a cyclic performance over 10 cycles. Lastly, our findings provide a new way to design solid-state electrolytes toward high-performance lithium–air batteries.

  12. Macroscopic Modeling of Polymer-Electrolyte Membranes

    SciTech Connect

    Weber, A.Z.; Newman, J.

    2007-04-01

    In this chapter, the various approaches for the macroscopic modeling of transport phenomena in polymer-electrolyte membranes are discussed. This includes general background and modeling methodologies, as well as exploration of the governing equations and some membrane-related topic of interest.

  13. Assessment of thin film batteries based on polymer electrolytes. Part 3: Specific energy versus specific power

    NASA Astrophysics Data System (ADS)

    Munshi, M. Z. A.; Owens, Boone B.

    1989-06-01

    The feasibility of solid state polymer electrolyte batteries for applications such as the electric vehicle depends on the variation in the performance levels of the specific energy and specific power. Efforts were centered mainly on rechargeable lithium batteries with electrolyte complexes formed between polyethylene oxide and lithium salts having an ionic conductivity of .0001 Ohms/cm and V6O13 insertion cathodes. Prismatic unit cells of variable cathode thicknesses have been modeled and calculated results indicate that high specific energies (approx. 700 W/kg) are possible for this battery system utilizing metallic current collectors. Considerably higher values result for low density metallized plastic current collectors.

  14. Three-dimensional network electrolytes with highly efficient ion-transporting channels for quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Shi, Jifu; Chen, Jiubin; Li, Yujian; Zhu, Yanqing; Xu, Gang; Xu, Jiayou

    2015-05-01

    Quasi-solid-state dye-sensitized solar cells (DSCs) are fabricated with three-dimensional network poly(adipic acid pentaerythritol ester) (PAAPE). The PAAPEs are prepared by esterification of pentaerythritol and adipic acid. This three-dimensional structure provides highly efficient ion-transporting channels for iodide/triiodide (I-/I3-) transport in the gel electrolyte. The optimized gel electrolyte shows conductivity of 4.03 mS cm-1 at 25 °C. The fabricated DSC obtains a photoenergy conversion efficiency of 6.81% under AM 1.5 irradiation.

  15. Enhanced Electrochemical Stability of Quasi-Solid-State Electrolyte Containing SiO2 Nanoparticles for Li-O2 Battery Applications.

    PubMed

    Kim, Hyunjin; Kim, Tae Young; Roev, Victor; Lee, Heung Chan; Kwon, Hyuk Jae; Lee, Hyunpyo; Kwon, Soonchul; Im, Dongmin

    2016-01-20

    A stable electrolyte is required for use in the open-packing environment of a Li-O2 battery system. Herein, a gelled quasi-solid-state electrolyte containing SiO2 nanoparticles was designed, in order to obtain a solidified electrolyte with a high discharge capacity and long cyclability. We successfully fabricated an organic-inorganic hybrid matrix with a gelled structure, which exhibited high ionic conductivity, thereby enhancing the discharge capacity of the Li-O2 battery. In particular, the improved electrochemical stability of the gelled cathode led to long-term cyclability. The organic-inorganic hybrid matrix with the gelled structure played a beneficial role in improving the ionic conductivity and long-term cyclability and diminished electrolyte evaporation. The experimental and theoretical findings both suggest that the preferential binding between amorphous SiO2 and polyethylene glycol dimethyl ether (PEGDME) solvent led to the formation of the solidified gelled electrolyte and improved electrochemical stability during cycling, while enhancing the stability of the quasi-solid state Li-O2 battery.

  16. Fabrication of ultrathin solid electrolyte membranes of β-Li3PS4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

    DOE PAGES

    Wang, Hui; Hood, Zachary D.; Xia, Younan; ...

    2016-04-25

    All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li3PS4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreased to achievemore » ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li3PS4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

  17. The Organic Solid State.

    ERIC Educational Resources Information Center

    Cowan, Dwaine O.; Wlygul, Frank M.

    1986-01-01

    Reviews interesting and useful electrical, magnetic, and optical properties of the organic solid state. Offers speculation as to areas of fruitful research. Discusses organic superconductors, conducting organic polymers, organic metals, and traces recent history of creation of organic metals. (JM)

  18. The Organic Solid State.

    ERIC Educational Resources Information Center

    Cowan, Dwaine O.; Wlygul, Frank M.

    1986-01-01

    Reviews interesting and useful electrical, magnetic, and optical properties of the organic solid state. Offers speculation as to areas of fruitful research. Discusses organic superconductors, conducting organic polymers, organic metals, and traces recent history of creation of organic metals. (JM)

  19. In situ gelation of Al(III)-4-tert-butylpyridine based metal-organic gel electrolyte for efficient quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Dong, Yu-Jie; Rao, Hua-Shang; Cao, Yang; Chen, Hong-Yan; Kuang, Dai-Bin; Su, Cheng-Yong

    2017-03-01

    A novel Al(III)-4-tert-butylpyridine (TBP) gel electrolyte is successfully achieved by a simple and facile in situ gelation method and applied as quasi-solid-state electrolyte for dye-sensitized solar cells (DSSCs). Through directly adding Al3+ into the TBP solution, the induced hydrolysis of Al3+ and the coordination interaction between Al3+ and TBP facilitates the formation of metal-organic gels(MOGs), in which such bi-functional TBP molecules will act as both gelators and active additives to tailor the performance of electrolytes. In addition, the gel electrolytes can largely preserve the properties of liquid electrolyte and penetrate well into the TiO2 photoanode film. Both Al3+ and TBP in the gel electrolytes affect the performance of cells. The Jsc of gel electrolytes decrease with the increasing concentration of gelators due to the enhanced strength and viscosity of the gel electrolytes, while the competition between Al3+ and TBP causes conduction band edge shift and electron recombination, leading to a variation of Voc. Herein, by tuning the molar ratio of Al3+/TBP, an impressive conversion efficiency of 8.25% is obtained, indicating a promising protocol of preparing MOGs not only to achieve high performance in solar cells, but also opens up extended scopes in other energy-related fields such as catalysis.

  20. A Novel Single-Ion-Conducting Polymer Electrolyte Derived from CO2-Based Multifunctional Polycarbonate.

    PubMed

    Deng, Kuirong; Wang, Shuanjin; Ren, Shan; Han, Dongmei; Xiao, Min; Meng, Yuezhong

    2016-12-14

    This work demonstrates the facile and efficient synthesis of a novel environmentally friendly CO2-based multifunctional polycarbonate single-ion-conducting polymer electrolyte with good electrochemistry performance. The terpolymerizations of CO2, propylene epoxide (PO), and allyl glycidyl ether (AGE) catalyzed by zinc glutarate (ZnGA) were performed to generate poly(propylene carbonate allyl glycidyl ether) (PPCAGE) with various alkene groups contents which can undergo clickable reaction. The obtained terpolymers exhibit an alternating polycarbonate structure confirmed by (1)H NMR spectra and an amorphous microstructure with glass transition temperatures (Tg) lower than 11.0 °C evidenced by differential scanning calorimetry analysis. The terpolymers were further functionalized with 3-mercaptopropionic acid via efficient thiol-ene click reaction, followed by reacting with lithium hydroxide, to afford single-ion-conducting polymer electrolytes with different lithium contents. The all-solid-state polymer electrolyte with the 41.0 mol % lithium containing moiety shows a high ionic conductivity of 1.61 × 10(-4) S/cm at 80 °C and a high lithium ion transference number of 0.86. It also exhibits electrochemical stability up to 4.3 V vs Li(+)/Li. This work provides an interesting design way to synthesize an all-solid-state electrolyte used for different lithium batteries.

  1. Inorganic-organic composite solid polymer electrolytes

    SciTech Connect

    Abraham, K.M.; Koch, V.R.; Blakley, T.J.

    2000-04-01

    Inorganic-organic composite solid polymer electrolytes (CSPEs) have been prepared from the poly(ethylene oxide) (PEO)-like electrolytes of the general formula polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP)-PEO{sub n}-LiX and Li{sup +}-conducting ceramic powders. In the PEO-like electrolytes, PVdF-HFP is the copolymer of PVdF and HFP, PEO{sub n} is a nonvolatile oligomeric polyethylene oxide of {approximately}400 g/mol molecular weight, and LiX is lithium bis(trifluoroethylsulfonyl)imide. Two types of inorganic oxide ceramic powders were used: a highly Li{sup +}-conducting material of the composition 14 mol % Li{sub 2}O-9Al{sub 2}O{sub 3}-38TiO{sub 2}-39P{sub 2}O{sub 5}, and the poorly Li{sup +}-conducting Li-silicates Li{sub 4{minus}x}M{sub x}SiO{sub 4} where M is Ca or Mg and x is 0 or 0.05. The composite electrolytes can be prepared as thin membranes in which the Li{sup +} conductivity and good mechanical strength of the Li{sup +}-conducting inorganic ceramics are complemented by the structural flexibility and high conductivity of organic polymer electrolytes. Excellent electrochemical and thermal stabilities have been demonstrated for the electrolyte films. Li//composite electrolyte//LiCoO{sub 2} rechargeable cells have been fabricated and cycled at room temperature and 50 C.

  2. Ternary polymer electrolytes containing pyrrolidinium-based polymeric ionic liquids for lithium batteries

    NASA Astrophysics Data System (ADS)

    Appetecchi, G. B.; Kim, G.-T.; Montanino, M.; Carewska, M.; Marcilla, R.; Mecerreyes, D.; De Meatza, I.

    The electrochemical properties of solvent-free, ternary polymer electrolytes based on a novel poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide polymeric ionic liquid (PIL) as polymer host and incorporating PYR 14TFSI ionic liquid and LiTFSI salt are reported. The PIL-LiTFSI-PYR 14TFSI electrolyte membranes were found to be chemically stable even after prolonged storage times in contact with lithium anode and thermally stable up to 300 °C. Particularly, the PIL-based electrolytes exhibited acceptable room temperature conductivity with wide electrochemical stability window, time-stable interfacial resistance values and good lithium stripping/plating performance. Preliminary battery tests have shown that Li/LiFePO 4 solid-state cells are capable to deliver above 140 mAh g -1 at 40 °C with very good capacity retention up to medium rates.

  3. The dielectric properties of polyindole -Zno containing LiClO4 polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Rajasudha, G.; Narayanan, V.; Stephen, A.

    2012-06-01

    The frequency dependent dielectric behaviour of composite polymer electrolyte (CPE) based on Polyindole with ZnO nano particles containing LiClO4 has been studied. The Impedance spectroscopy studies were obtained from 5MHz to 1Hz over the temperature range of 40°-100°C. The high dielectric permittivity values observed at low frequency region can be attributed to the space charge built near the electrode-electrolyte interface which blocks the charge transport. At higher frequencies, the permittivity values of the CPE were found to decrease rapidly and saturate, as the dipoles in the macromolecules hardly be able to orient in the direction of the applied field. These features make the electrolyte quite convenient for the development of advanced, solid-state, rechargeable lithium polymer batteries.

  4. Enhanced ionic conductivity and optical studies of plasticized (PEO-KCl) solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Chapi, Sharanappa; H, Devendrappa

    2015-06-01

    Solid polymer electrolytes (SPEs) based on Polyethylene oxide (PEO) doped with potassium chloride (KCl) were prepared by the solution cast technique. The conductivity increases from 10-10 to 10-6 Scm-1 at 303K with dopant. Optical absorption study shows that the direct & indirect optical band gaps were found decreased from 5.45-4.46eV and 4.96-3.86eV respectively with increasing the KCl. The XRD patterns reveal increasing the amorphous with increasing the dopent. The obtained results suggest that, these polymer systems are suitable candidates for solid state battery, electro chromic devices & optoelectronics display etc.

  5. Electrolytic hydrogen fuel production with solid polymer electrolyte technology.

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.; Fickett, A. P.

    1973-01-01

    A water electrolysis technology based on a solid polymer electrolyte (SPE) concept is presented for applicability to large-scale hydrogen production in a future energy system. High cell current density operation is selected for the application, and supporting cell test performance data are presented. Demonstrated cell life data are included to support the adaptability of the SPE system to large-size hydrogen generation utility plants as needed for bulk energy storage or transmission. The inherent system advantages of the acid SPE electrolysis technology are explained. System performance predictions are made through the year 2000, along with plant capital and operating cost projections.

  6. Electrolytic hydrogen fuel production with solid polymer electrolyte technology.

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.; Fickett, A. P.

    1973-01-01

    A water electrolysis technology based on a solid polymer electrolyte (SPE) concept is presented for applicability to large-scale hydrogen production in a future energy system. High cell current density operation is selected for the application, and supporting cell test performance data are presented. Demonstrated cell life data are included to support the adaptability of the SPE system to large-size hydrogen generation utility plants as needed for bulk energy storage or transmission. The inherent system advantages of the acid SPE electrolysis technology are explained. System performance predictions are made through the year 2000, along with plant capital and operating cost projections.

  7. Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

    NASA Astrophysics Data System (ADS)

    Lu, Canhui; Zhang, Xinxing; Zhang, Wei

    2015-05-01

    The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.

  8. Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

    SciTech Connect

    Lu, Canhui; Zhang, Xinxing; Zhang, Wei

    2015-05-22

    The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.

  9. Nano-CdS by polymer-inorganic solid-state reaction: Visible light pristine photocatalyst for hydrogen generation

    SciTech Connect

    Kanade, K.G.; Baeg, Jin-OoK . E-mail: jobaeg@krict.re.kr; Mulik, U.P.; Amalnerkar, D.P.; Kale, B.B. . E-mail: kbbb1@yahoo.com

    2006-12-14

    We have explored the possibility of using environmentally stable nano-CdS embedded in thermally stable polymer matrix as an efficient photocatalyst for the hydrogen generation by photodecomposition of hydrogen sulphide under visible light irradiation. Initially, we restricted our attempt to the usage of nano-CdS synthesized by novel polymer-inorganic solid-state reaction between cadmium iodide and polyphenylene sulphide (PPS). The structural study revealed the formation of nanocrystallites of CdS with the particle size ranging from 6 to 28 nm entrapped in modified (cyclized) PPS matrix. A quantum yield of 19.7% for the H{sub 2} generation was accomplished with CdS-PPS nanocomposite in pristine state, which appears to be superior in comparison to that of the conventional Pt loaded CdS. We believe that this straightforward approach can be extended to synthesise other nano-metal sulphides in polymer network for photocatalytic and allied applications.

  10. Solid-state voltammetry and self-diffusion dynamics of a linear monotagged redox polymer:. omega. -ferrocenecarboxamido-. alpha. -methoxypoly(ethylene oxide)

    SciTech Connect

    Pinkerton, M.J.; Le Mest, Y.; Zhang, H.; Watanabe, M.; Murray, R.W. )

    1990-05-09

    The synthesized title labeled polymer, Fc-MePEG, MW = 2,590, analytically characterized as free of unlabeled PEO and of ferrocene monomer, dissolves LiClO{sub 4} electrolyte and in dry undiluted form is both a polymer electrolyte and an electroactive phase. The microelectrode solid-state voltammetrically measured, center-of-mass self-diffusion coefficient for Fc-MePEG in its polymer let, 1.3 {times} 10{sup {minus}8} cm{sup 2}/s at 62{degree}C, is 3.4 times smaller than that for ferrocene monomer dissolved in unlabeled (MW = 2,380) Me{sub 2}PEG. Electron hopping is estimated to contribute less than 10% to the diffusion rates of Fc-MePEG and of monomer dissolved at 40-50 mM concentrations in unlabeled Me{sub 2}PEG. At room temperature, where Fc-MePEG and Me{sub 2}PEG are waxy solids, D{sub Fc-MePEG} is 3.9 {times} 10{sup {minus}12} cm{sup 2}/s, 12 times smaller than that of monomer ferrocene, in Me{sub 2}PEG, and which corresponds to a diffusion pathlength of ca. 110-200 nm during the electrochemical experiment. Dissolved in CH{sub 3}CN or CH{sub 2}Cl{sub 2}, Fe-MePEG diffuses 8-10 times more slowly than ferrocene monomer which is consistent with transport as a random coiled sphere.

  11. Enhancing the high rate capability and cycling stability of LiMn₂O₄ by coating of solid-state electrolyte LiNbO₃.

    PubMed

    Zhang, Zhi-Jia; Chou, Shu-Lei; Gu, Qin-Fen; Liu, Hua-Kun; Li, Hui-Jun; Ozawa, Kiyoshi; Wang, Jia-Zhao

    2014-12-24

    To study the influence of solid-state electrolyte coating layers on the performance of cathode materials for lithium-ion batteries in combination with organic liquid electrolyte, LiNbO3-coated Li1.08Mn1.92O4 cathode materials were synthesized by using a facile solid-state reaction method. The 0.06LiNbO3-0.97Li1.08Mn1.92O4 cathode exhibited an initial discharge capacity of 125 mAh g(-1), retaining a capacity of 119 mAh g(-1) at 25 °C, while at 55 °C, it exhibited an initial discharge capacity of 130 mAh g(-1), retaining a capacity of 111 mAh g(-1), both at a current density of 0.5 C (where 1 C is 148 mAh g(-1)). Very good rate capability was demonstrated, with the 0.06LiNbO3-0.97Li1.08Mn1.92O4 cathode showing more than 85% capacity at the rate of 50 C compared with the capacity at 0.5 C. The 0.06LiNbO3-0.97Li1.08Mn1.92O4 cathode showed a high lithium diffusion coefficient (1.6 × 10(-10) cm(2) s(-1) at 55 °C), and low apparent activation energy (36.9 kJ mol(-1)). The solid-state electrolyte coating layer is effective for preventing Mn dissolution and maintaining the high ionic conductivity between the electrode and the organic liquid electrolyte, which may improve the design and construction of next-generation large-scale lithium-ion batteries with high power and safety.

  12. A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte

    NASA Astrophysics Data System (ADS)

    Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

    2016-06-01

    A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating

  13. A supramolecular gel electrolyte formed from amide based co-gelator for quasi-solid-state dye-sensitized solar cell with boosted electron kinetic processes

    NASA Astrophysics Data System (ADS)

    Huo, Zhipeng; Wang, Lu; Tao, Li; Ding, Yong; Yi, Jinxin; Alsaedi, Ahmed; Hayat, Tasawar; Dai, Songyuan

    2017-08-01

    A supramolecular gel electrolyte (Tgel > 100 °C) is formed from N,N‧-1,8-octanediylbis-dodecanamide and iodoacetamide as two-component co-gelator, and introduced into the quasi-solid-state dye-sensitized solar cells (QS-DSSCs). The different morphologies of microscopic network between two-component and single-component gel electrolytes have influence on the diffusion of redox couple in gel electrolytes and further affect the electron kinetic processes in QS-DSSCs. Compared with the single-component gel electrolyte, the two-component gel electrolyte has less compact gel network and weaker steric hindrance effect, which provides more effective charge transport channel for the diffusion of I3/I- redox couple. Meanwhile, the sbnd NH2 groups of iodoacetamide molecules interact with Li+ and I3-, which also accelerate the transport of I3-/I- and decrease in the I3- concentration in the TiO2/electrolyte interface. As a result, nearly a 12% improvement in short-circuit photocurrent density (Jsc) and much higher open circuit potential (Voc) are found in the two-component gel electrolyte based QS-DSSC. Consequently, the QS-DSSC based on the supramolecular gel electrolyte obtains a 17% enhancement in the photoelectric conversion efficiency (7.32%) in comparison with the QS-DSSC based on the single-component gel electrolyte (6.24%). Furthermore, the degradations of these QS-DSSCs are negligible after one sun light soaking with UV cutoff filter at 50 °C for 1000 h.

  14. All-solid-state lithium secondary batteries using NiS-carbon fiber composite electrodes coated with Li₂S-P₂S₅ solid electrolytes by pulsed laser deposition.

    PubMed

    Aso, Keigo; Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2013-02-01

    Composite materials including NiS active materials, sulfide-based solid electrolytes (SE), and conductive additives (VGCF: vapor grown carbon fiber) were prepared by coating a highly conductive Li(2)S-P(2)S(5) solid electrolyte onto NiS-VGCF composite using pulsed laser deposition (PLD). From scanning electron microscopy, NiS nanoparticles were on VGCF surface after coating of solid electrolytes using PLD. All-solid-state cells using the SE-coated NiS-VGCF composite and the uncoated NiS-VGCF composite were fabricated, and then the coating effects on the electrochemical performance by forming the SE thin film onto the NiS-VGCF composite were investigated. At a high current density of 3.8 mA cm(-2) (corresponding to ca. 1 C), an all-solid-state cell fabricated using the SE-coated NiS-VGCF composite as a working electrode showed the initial discharge capacity of 300 mA h g(-1), and exhibited better cycle performance than the cell using the uncoated NiS-VGCF composite.

  15. Materials space of solid-state electrolytes: unraveling chemical composition-structure-ionic conductivity relationships in garnet-type metal oxides using cheminformatics virtual screening approaches.

    PubMed

    Kireeva, Natalia; Pervov, Vladislav S

    2017-08-09

    The organic electrolytes of most current commercial rechargeable Li-ion batteries (LiBs) are flammable, toxic, and have limited electrochemical energy windows. All-solid-state battery technology promises improved safety, cycling performance, electrochemical stability, and possibility of device miniaturization and enables a number of breakthrough technologies towards the development of new high power and energy density microbatteries for electronics with low processing cost, solid oxide fuel cells, electrochromic devices, etc. Currently, rational materials design is attracting significant attention, which has resulted in a strong demand for methodologies that can accelerate the design of materials with tailored properties; cheminformatics can be considered as an efficient tool in this respect. This study was focused on several aspects: (i) identification of the parameters responsible for high Li-ion conductivity in garnet structured oxides; (ii) development of quantitative models to elucidate composition-structure-Li ionic conductivity relationships, taking into account the experimental details of sample preparation; (iii) circumscription of the materials space of solid garnet-type electrolytes, which is attractive for virtual screening. Several candidate compounds have been recommended for synthesis as potential solid state electrolyte materials.

  16. Improved Fabrication Of Cathodes For Solid-State Li Cells

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan

    1995-01-01

    Utilization of cathode material increased. Improved composite-cathode/polymer-electrolyte units for solid-state lithium secondary electrochemical cells fabricated in modified version of original method of fabrication. Further development of units may lead to increases in energy and power densities and in cycle lives of rechargeable lithium cells.

  17. Scalable plasticized polymer electrolytes reinforced with surface-modified sepiolite fillers - A feasibility study in lithium metal polymer batteries

    NASA Astrophysics Data System (ADS)

    Mejía, Alberto; Devaraj, Shanmukaraj; Guzmán, Julio; Lopez del Amo, Juan Miguel; García, Nuria; Rojo, Teófilo; Armand, Michel; Tiemblo, Pilar

    2016-02-01

    Electrochemical properties of (polyethylene oxide) (PEO)/lithium trifluoromethanesulfonate (LiTf)/ethylene carbonate (EC)/sepiolite extruded composite electrolytes were studied. Appreciable electrochemical stability of 4.5 V at 70 °C was observed for polymer composite membranes with D-α-tocopherol-polyethylene glycol 1000 succinate-coated sepiolite fillers. Lithium plating/stripping analysis indicated no evidence of dendrite formation with good interfacial properties which were further confirmed by postmortem analysis of the cells. Solid state NMR studies show the presence of two Li+ population in the membranes. The feasibility of these electrolytes has been shown with LiFePO4 cathode materials. Initial discharge capacity of 142 mAh/g was observed remaining at 110 mAh/g after 25 cycles with a coulombic efficiency of 96%. The upscaling of these polymers can be easily achieved by extrusion technique and the capacity can be improved by varying the cathode architecture.

  18. Stretchable, Weavable Coiled Carbon Nanotube/MnO2/Polymer Fiber Solid-State Supercapacitors

    PubMed Central

    Choi, Changsoon; Kim, Shi Hyeong; Sim, Hyeon Jun; Lee, Jae Ah; Choi, A Young; Kim, Youn Tae; Lepró, Xavier; Spinks, Geoffrey M.; Baughman, Ray H.; Kim, Seon Jeong

    2015-01-01

    Fiber and yarn supercapacitors that are elastomerically deformable without performance loss are sought for such applications as power sources for wearable electronics, micro-devices, and implantable medical devices. Previously reported yarn and fiber supercapacitors are expensive to fabricate, difficult to upscale, or non-stretchable, which limits possible use. The elastomeric electrodes of the present solid-state supercapacitors are made by using giant inserted twist to coil a nylon sewing thread that is helically wrapped with a carbon nanotube sheet, and then electrochemically depositing pseudocapacitive MnO2 nanofibers. These solid-state supercapacitors decrease capacitance by less than 15% when reversibly stretched by 150% in the fiber direction, and largely retain capacitance while being cyclically stretched during charge and discharge. The maximum linear and areal capacitances (based on active materials) and areal energy storage and power densities (based on overall supercapacitor dimensions) are high (5.4 mF/cm, 40.9 mF/cm2, 2.6 μWh/cm2 and 66.9 μW/cm2, respectively), despite the engineered superelasticity of the fiber supercapacitor. Retention of supercapacitor performance during large strain (50%) elastic deformation is demonstrated for supercapacitors incorporated into the wristband of a glove. PMID:25797351

  19. Stretchable, Weavable Coiled Carbon Nanotube/MnO2/Polymer Fiber Solid-State Supercapacitors

    NASA Astrophysics Data System (ADS)

    Choi, Changsoon; Kim, Shi Hyeong; Sim, Hyeon Jun; Lee, Jae Ah; Choi, A. Young; Kim, Youn Tae; Lepró, Xavier; Spinks, Geoffrey M.; Baughman, Ray H.; Kim, Seon Jeong

    2015-03-01

    Fiber and yarn supercapacitors that are elastomerically deformable without performance loss are sought for such applications as power sources for wearable electronics, micro-devices, and implantable medical devices. Previously reported yarn and fiber supercapacitors are expensive to fabricate, difficult to upscale, or non-stretchable, which limits possible use. The elastomeric electrodes of the present solid-state supercapacitors are made by using giant inserted twist to coil a nylon sewing thread that is helically wrapped with a carbon nanotube sheet, and then electrochemically depositing pseudocapacitive MnO2 nanofibers. These solid-state supercapacitors decrease capacitance by less than 15% when reversibly stretched by 150% in the fiber direction, and largely retain capacitance while being cyclically stretched during charge and discharge. The maximum linear and areal capacitances (based on active materials) and areal energy storage and power densities (based on overall supercapacitor dimensions) are high (5.4 mF/cm, 40.9 mF/cm2, 2.6 μWh/cm2 and 66.9 μW/cm2, respectively), despite the engineered superelasticity of the fiber supercapacitor. Retention of supercapacitor performance during large strain (50%) elastic deformation is demonstrated for supercapacitors incorporated into the wristband of a glove.

  20. Preliminary Evaluations of Polymer-based Lithium Battery Electrolytes Under Development for the Polymer Electrolyte Rechargeable Systems Program

    NASA Technical Reports Server (NTRS)

    Manzo, Michelle A.; Bennett, William R.

    2003-01-01

    A component screening facility has been established at The NASA Glenn Research Center (GRC) to evaluate candidate materials for next generation, lithium-based, polymer electrolyte batteries for aerospace applications. Procedures have been implemented to provide standardized measurements of critical electrolyte properties. These include ionic conductivity, electronic resistivity, electrochemical stability window, cation transference number, salt diffusion coefficient and lithium plating efficiency. Preliminary results for poly(ethy1ene oxide)-based polymer electrolyte and commercial liquid electrolyte are presented.

  1. Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

    NASA Astrophysics Data System (ADS)

    Crowe, Adam J.; Bartlett, Bart M.

    2016-10-01

    With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg2+), relative to lithium-ion (Li+) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg2+, improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recent advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes.

  2. Performance limitations of polymer electrolytes based on ethylene oxide polymers.

    SciTech Connect

    Buriez, Olivier; Han, Yong Bong; Hou, Jun; Kerr, John B.; Qiao, Jun; Sloop, Steven E.; Tian, Minmin; Wang, Shanger

    1999-10-07

    Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5 x 10-5 S/cm at 25 C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5-6 units long there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles.

  3. Ionic conductivity in PEO-KOH polymer electrolytes and electrochemical cell performance

    NASA Astrophysics Data System (ADS)

    Hassan, M. F.; Arof, A. K.

    2005-10-01

    Polyethylene oxide (PEO) and potassium hydroxide (KOH) alkaline solid polymer electrolytes were prepared by the solution cast technique. The PEO:KOH wt% ratio in the alkaline solid polymer electrolyte system which exhibits the highest room temperature conductivity is 60:40. The conductivity was 3.10 × 10-5 S cm-1. X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS) were used to study the characteristics of the PEO polymer electrolyte films. The Rice and Roth model was used to evaluate the number density of charge carriers. Knowing the number density of charge carriers enabled the mobility and diffusion coefficient to be calculated. An all solid-state Ni(OH)2/MH rechargeable metal hydride cell has been fabricated using the highest conducting PEO-KOH alkaline solid polymer electrolyte. The cell was charged at a constant current of 2 mA and discharged at 0.5 mA. The discharge characteristics improved upon cycling and the plateau voltage maintained above 1.3 V for more than 2 hours during the 16th cycle.

  4. Compositional effect investigation by addition PEG, PEO plasticiser of LiBOB based solid polymer electrolyte for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sabrina, Qolby; Ratri, Christin Rina

    2017-08-01

    Development polymer electrolyte with high ionic conductivity is main of object in solid state electrolyte will be potential application as electrolyte batteries. Casting method have been used to prepared solid polymer electrolyte. Adding polyethylene(glycol) PEG and Poly(ethylene oxide) PEO as polymer matrix be made of poly(vinylidene fluoride) (PVdF) and lithium bis(oxalato) borate (LiBOB) to improve structure morphology and impedance characterization of solid electrolyte. The ratio of PEG and PEO is varied to study effect on the conductivity. Electro impedance spectroscopy (EIS) studies are carried out on the prepared samples. The impedance measurement show that the conductivity with composition PVdF- PEG- LiBOB 10% better than the other varieties to applied as solid electrolyte batteries. SEM morphology PVdF- PEG- LiBOB 10% sample showed the low crystallinity was caused by interaction between lithium salt and polymer. With their properties the solid polymer electrolyte are considered as promising candidates of applications for lithium ion batteries.

  5. Solid state oxygen sensor

    DOEpatents

    Garzon, Fernando H.; Chung, Brandon W.; Raistrick, Ian D.; Brosha, Eric L.

    1996-01-01

    Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer.

  6. Solid state oxygen sensor

    DOEpatents

    Garzon, F.H.; Chung, B.W.; Raistrick, I.D.; Brosha, E.L.

    1996-08-06

    Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer. 4 figs.

  7. Development of molecularly imprinted polymers as tailored templates for the solid-state [2+2] photodimerization.

    PubMed

    Wu, Xiangyang; Shimizu, Ken D

    2009-11-15

    In this study, a molecularly imprinted polymer (MIP) was prepared to selectively template the [2+2] photodimerization of trans-1,2-bis(4-pyridyl)ethylene. First, an MIP selective for rctt-tetrakis(4-pyridyl)cyclobutane, which is the [2+2] photodimerization product of trans-1,2-bis(4-pyridyl)ethylene, was prepared from methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA). The non-covalent MIP showed enhanced affinity for both the templating agent, rctt-tetrakis(4-pyridyl)cyclobutane, and the alkene precursor, trans-1,2-bis(4-pyridyl)ethylene. The solid-state photodimerization reaction proceeded in significantly higher yields in the presence of the MIP. Control reactions carried out in the absence of polymer gave no product, and reactions carried out in the presence of a non-imprinted polymer and an MIP imprinted with a different template, 3-hydroxymethylpyridine, gave much lower yields of the cyclobutane photodimerization product. The outcome of the MIP-templated photodimerization reaction was strongly influenced by the binding site heterogeneity of the non-covalently imprinted polymers. For example, higher yields were observed with decreasing olefin loadings levels on the MIPs. This binding site heterogeneity was characterized via application of the Freundlich binding model to the experimentally measured binding isotherms. These confirmed that the non-covalent MIPs had very few high-affinity binding sites, which greatly limits the capacity and ultimately the utility of these materials as templates in synthetic organic applications.

  8. Ionic Transport Across Interfaces of Solid Glass and Polymer Electrolytes

    SciTech Connect

    Tenhaeff, Wyatt E; Yu, Xiang; Hong, Kunlun; Perry, Kelly A; Dudney, Nancy J

    2011-01-01

    A study of lithium cation transport across solid-solid electrolyte interfaces to identify critical resistances in nanostructured solid electrolytes is reported. Bilayers of glass and polymer thin film electrolytes were fabricated and characterized for this study. The glass electrolyte was lithium phosphorous oxynitride (Lipon), and two polymer electrolytes were studied: poly(methyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate) and poly(styrene-co-poly(ethylene glycol) methyl ether methacrylate). Both copolymers contained LiClO{sub 4} salt. In bilayers where polymer electrolyte layers are fabricated on top of Lipon, the interfacial resistance dominates transport. At 25 C, the interfacial resistance is at least three times greater than the sum of the Lipon and polymer electrolyte resistances. By reversing the structure and fabricating Lipon on top of the polymer electrolytes, the interfacial resistance is eliminated. Experiments to elucidate the origin of the interfacial resistance in the polymer-on-Lipon bilayers reveal that the solvent mixtures used to fabricate the polymer layers do not degrade the Lipon layer. The importance of the polymer electrolytes' mechanical properties is also discussed.

  9. Sol-Gel-Derived Lithium Superionic Conductor Li1.5Al0.5Ge1.5(PO4)3 Electrolyte for Solid-State Lithium-Oxygen Batteries

    DTIC Science & Technology

    2014-03-12

    AFRL-RQ-WP-TP-2015-0055 SOL-GEL-DERIVED LITHIUM SUPERIONIC CONDUCTOR LI1.5AL0.5GE1.5(PO4)3 ELECTROLYTE FOR SOLID -STATE LITHIUM -OXYGEN...2014 4. TITLE AND SUBTITLE SOL-GEL-DERIVED LITHIUM SUPERIONIC CONDUCTOR LI1.5AL0.5GE1.5(PO4)3 ELECTROLYTE FOR SOLID -STATE LITHIUM -OXYGEN BATTERIES...attracting a great deal of attention as a solid electrolyte for lithium -oxygen (Li- O2) batteries due to its high ionic conductivity. In this study, LAGP

  10. On the chemical stability of post-lithiated garnet Al-stabilized Li7La3Zr2O12 solid state electrolyte thin films

    NASA Astrophysics Data System (ADS)

    Rawlence, Michael; Garbayo, Inigo; Buecheler, Stephan; Rupp, J. L. M.

    2016-08-01

    Garnet-based Al-doped Li7La3Zr2O12 has the potential to be used as a solid state electrolyte for future lithium microbattery architectures, due to its relatively high Li+ conductivity and stability against Li. Through this work, a model experiment is presented in which the effect of post-lithiation on phase formation and chemical stability is studied for pulsed laser deposited Al-doped Li7La3Zr2O12 thin films on MgO substrates. We report the implications of the newly suggested post-lithiation route for films with thicknesses between 90 and 380 nm. The phase changes from cubic, to a mix of cubic and tetragonal Li7La3Zr2O12, to a cubic Li7La3Zr2O12 and La2Zr2O7 containing film is accompanied by a reduction in the degree of de-wetting as the thickness increases. This study reveals that the thicker, dense, and continuous films remain predominantly in a mixed phase containing cubic Li7La3Zr2O12 and the lithium free La2Zr2O7 phase whereas the thinner, de-wetted films exhibit improved lithium incorporation resulting in the absence of the lithium free phase. For tuning the electrical conductivity and effective use of these structures in future batteries, understanding this material system is of great importance as the chemical stability of the cubic Li7La3Zr2O12 phase in the thin film system will control its effective use. We report a conductivity of 1.2 × 10-3 S cm-1 at 325 °C for a 380 nm thick solid state electrolyte film on MgO for potential operation in future all solid state battery assemblies.Garnet-based Al-doped Li7La3Zr2O12 has the potential to be used as a solid state electrolyte for future lithium microbattery architectures, due to its relatively high Li+ conductivity and stability against Li. Through this work, a model experiment is presented in which the effect of post-lithiation on phase formation and chemical stability is studied for pulsed laser deposited Al-doped Li7La3Zr2O12 thin films on MgO substrates. We report the implications of the newly

  11. The use of 6Li{7Li}-REDOR NMR spectroscopy to compare the ionic conductivities of solid-state lithium ion electrolytes.

    PubMed

    Spencer, T L; Plagos, N W; Brouwer, D H; Goward, G R

    2014-02-14

    Garnet-like solid-state electrolyte materials for lithium ion batteries are promising replacements for the currently-used liquid electrolytes. This work compares the temperature dependent Li(+) ion hopping rate in Li6BaLa2M2O12 (M = Ta, Nb) using solid-state (6)Li{(7)Li}-REDOR NMR. The slope of the (6)Li{(7)Li}-REDOR curve is highly temperature dependent in these two phases, and a comparison of the changes of the REDOR slopes as a function of temperature has been used to evaluate the Li(+) ion dynamics. Our results indicate that the Nb phase has a higher overall ionic conductivity in the range of 247 K to 350 K, as well as a higher activation energy for lithium ion hopping than the Ta counterpart. For appropriate relative timescales of the dipolar couplings and ion transport processes, this is shown to be a facile method to compare ion dynamics among similar structures.

  12. Solid polymer electrolyte composite membrane comprising laser micromachined porous support

    DOEpatents

    Liu, Han [Waltham, MA; LaConti, Anthony B [Lynnfield, MA; Mittelsteadt, Cortney K [Natick, MA; McCallum, Thomas J [Ashland, MA

    2011-01-11

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 5 microns, are made by laser micromachining and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

  13. Synthesis and characterizations of novel polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Chanthad, Chalathorn

    Polymer electrolytes are an important component of many electrochemical devices. The ability to control the structures, properties, and functions of polymer electrolytes remains a key subject for the development of next generation functional polymers. Taking advantage of synthetic strategies is a promising approach to achieve the desired chemical structures, morphologies, thermal, mechanical, and electrochemical properties. Therefore, the major goal of this thesis is to develop synthetic methods for of novel proton exchange membranes and ion conductive membranes. In Chapter 2, new classes of fluorinated polymer- polysilsesquioxane nanocomposites have been designed and synthesized. The synthetic method employed includes radical polymerization using the functional benzoyl peroxide initiator for the telechelic fluorinated polymers with perfluorosulfonic acids in the side chains and a subsequent in-situ sol-gel condensation of the prepared triethoxylsilane-terminated fluorinated polymers with alkoxide precursors. The properties of the composite membranes have been studied as a function of the content and structure of the fillers. The proton conductivity of the prepared membranes increases steadily with the addition of small amounts of the polysilsesquioxane fillers. In particular, the sulfopropylated polysilsesquioxane based nanocomposites display proton conductivities greater than Nafion. This is attributed to the presence of pendant sulfonic acids in the fillers, which increases ion-exchange capacity and offers continuous proton transport channels between the fillers and the polymer matrix. The methanol permeability of the prepared membranes has also been examined. Lower methanol permeability and higher electrochemical selectivity than those of Nafion have been demonstrated in the polysilsesquioxane based nanocomposites. In Chapter 3, the synthesis of a new class of ionic liquid-containing triblock copolymers with fluoropolymer mid-block and imidazolium methacrylate

  14. International Symposium on Polymer Electrolytes (3rd) Held in Annecy, France on June 17-21, 1991. Extended Abstracts

    DTIC Science & Technology

    1991-06-01

    Quimidca - Universidade. federal de. Sao Carlos - B~rasil. 2 - Instituto de Fisica e Quimica de Sao Carlos - BrasiL. SOLID STATE ELECTROCHROMIC DISPLAY...odense, Denaxk EFFECT OF PL4SrICIZERS ON THE PROPERTIES OF A NEW AMBIENT TEMPERATURE POLYMER ELECTROLYTE 4 page: 119 13 D. rDAmIL 1 ,. nGALTHIER2...and evaporating the solvents first at ambient temperature and finally under reduced pressure at 500 C for at least 48 hrs. The complexes were

  15. Toward Higher Energy Conversion Efficiency for Solid Polymer Electrolyte Dye-Sensitized Solar Cells: Ionic Conductivity and TiO2 Pore-Filling.

    PubMed

    Song, Donghoon; Cho, Woohyung; Lee, Jung Hyun; Kang, Yong Soo

    2014-04-03

    Even though the solid polymer electrolyte has many intrinsic advantages over the liquid electrolyte, its ionic conductivity and mesopore-filling are much poorer than those of the liquid electrolyte, limiting its practical application to electrochemical devices such as dye-sensitized solar cells (DSCs). Two major shortcomings associated with utilizing solid polymer electrolytes in DSCs are first discussed, low ionic conductivity and poor pore-filling in mesoporous photoanodes for DSCs. In addition, future directions for the successful utilization of solid polymer electrolytes toward improving the performance of DSCs are proposed. For instance, the facilitated mass-transport concept could be applied to increase the ionic conductivity. Modified biphasic and triple-phasic structures for the photoanode are suggested to take advantage of both the liquid- and solid-state properties of electrolytes.

  16. Use of nafion as a solid polymer electrolyte for the electroreduction of tungsten (VI) fluoride

    SciTech Connect

    Bettelheim, A.; Raven, A.; Polak, M.; Ozer, D. )

    1992-01-01

    In this paper a new method is described in which WF{sub 6} is electroreduced in a solid-state cell configuration with a Nafion membrane serving as a solid polymer electrolyte. Cyclic voltammetry indicates a behavior similar to that of metallic tungsten for coatings obtained at dry conditions and similar to that of tungsten oxide species when water vapor is not totally expelled. Surface analysis using Auger electroscope and x-ray photoelectron spectroscopy shows that solid-state electro-reduction of WF{sub 6} in dry conditions yields coatings free of fluorine, which contain much less oxygen than electrodeposits obtained from aqueous solutions. However, due to possible oxidation and reduction reactions occurring before and during the surface-analysis process, it is not possible at this state to determine the exact content of metallic and oxide species in the deposits obtained by the present method.

  17. Conductivity and Stability of Photopolymerized Polymer Electrolyte Network

    NASA Astrophysics Data System (ADS)

    Kyu, Thein; He, Ruixuan; Chen, Yu-Ming; Mao, Jialin; Zhu, Yu; Kyu'S Group, , Dr.; Zhu'S Group Collaboration, , Dr.

    2014-03-01

    A melt-processing window has been identified within the wide isotropic region of the phase diagram of ternary blends consisting of poly (ethylene glycol diacrylate) (PEGDA), tetraethylene glycol dimethyl ether (TEGDME) and lithium bis(trifluoromethane) sulfonamide (LiTFSI). Upon UV-crosslinking of PEGDA in the isotropic window, the polymer electrolyte membrane (PEM) network thus formed is completely transparent and remains in the single phase without undergoing polymerization-induced phase separation or polymerization-induced crystallization. These PEM networks are solid albeit flexible and light-weight with safety and space saving attributes. The ionic conductivity as determined by AC impedance spectroscopy exhibited very high room-temperature ionic conductivity on the order of ~10-3 S/cm in several compositions, viz., 10/45/45, 20/40/40 and 30/35/35 PEGDA/TEGDME/LiTFSI networks. Cyclic voltammetry measurement of these solid-state PEM networks revealed excellent electrochemical stability against lithium reference electrode. The above study has been extended to the anode (graphite) and cathode (LiFePO4) half-cell configurations with lithium as counter electrode. Charge/discharge cycling behavior of these half cells will be discussed. Supported by NSF-DMR 1161070 and University of Akron.

  18. New composite polymer electrolyte comprising mesoporous lithium aluminate nanosheets and PEO/LiClO 4

    NASA Astrophysics Data System (ADS)

    Hu, Linfeng; Tang, Zilong; Zhang, Zhongtai

    Mesoporous materials, due to its potential for advanced applications in catalysis and nanoscience, have attracted much attention in the past decade. In this work, mesoporous lithium aluminate (next called MLA) nanosheets with high specific surface area were prepared by a hydrothermal method using hex-adecyltrimethyl ammonium bromide (CTAB) as the template. A novel PEO-based composite polymer electrolyte has been developed by using MLA powders as the filler. The electrochemical impedance showed that the conductivity was improved simultaneously. A high conductivity of 2.24 × 10 -5 S cm -1 at 25 °C was obtained. The lithium polymer battery using this novel composite polymer electrolyte and with lithium metal and LiFePO 4 employed as anode and cathode, respectively, showed high discharge capacity (more than 140 mAh g -1 at 60 °C) and excellent cycling stability as revealed by galvanostastically charge/discharge cycling tests. The excellent electrochemical performances at low temperature of the cells were obtained, which was attributed to the high surface area and channels structure of the filler. The excellent properties of the solid-state lithium battery suggested that, PEO 16-LiClO 4-MLA composite polymer electrolyte can be used as a candidate material for lithium polymer batteries.

  19. Solid-polymer-electrolyte fuel cells

    SciTech Connect

    Fuller, T.F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich's solution and analysis.

  20. Solid-polymer-electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Fuller, T. F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25 C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich's solution and analysis.

  1. Mathematical modeling of polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Sousa, Ruy; Gonzalez, Ernesto R.

    Fuel cells with a polymer electrolyte membrane have been receiving more and more attention. Modeling plays an important role in the development of fuel cells. In this paper, the state-of-the-art regarding modeling of fuel cells with a polymer electrolyte membrane is reviewed. Modeling has allowed detailed studies concerning the development of these cells, e.g. in discussing the electrocatalysis of the reactions and the design of water-management schemes to cope with membrane dehydration. Two-dimensional models have been used to represent reality, but three-dimensional models can cope with some important additional aspects. Consideration of two-phase transport in the air cathode of a proton exchange membrane fuel cell seems to be very appropriate. Most fuel cells use hydrogen as a fuel. Besides safety concerns, there are problems associated with production, storage and distribution of this fuel. Methanol, as a liquid fuel, can be the solution to these problems and direct methanol fuel cells (DMFCs) are attractive for several applications. Mass transport is a factor that may limit the performance of the cell. Adsorption steps may be coupled to Tafel kinetics to describe methanol oxidation and methanol crossover must also be taken into account. Extending the two-phase approach to the DMFC modeling is a recent, important point.

  2. Solid-State Constitutive Modelling of Glassy Polymers: Coupling the Rolie-Poly Equations for Melts with Anisotropic Viscoplastic Flow

    NASA Astrophysics Data System (ADS)

    De Focatiis, Davide S. A.; Embery, John; Buckley, C. Paul

    2008-07-01

    This paper investigates the behaviour of a well-characterised monodisperse grade of entangled atactic polystyrene across a very wide temperature and strain rate range through linear and non-linear melt rheology and solid-state deformation. In an effort to construct a constitutive model for large deformations able to describe rheological response right across this wide timescale, two well-established rheological models are combined: the well known RoliePoly (RP) conformational melt model and the Oxford glass-rubber constitutive model for glassy polymers. Comparisons between experimental data and simulations from a numerical implementation of the model illustrate that the model can cope well with the range of deformations in which orientation is limited to length-scales longer than an entanglement length. One approach in which the model can be expanded to incorporate the effects of orientation on shorter length scales using anisotropic viscoplastic flow is briefly discussed.

  3. Solid-State Constitutive Modelling of Glassy Polymers: Coupling the Rolie-Poly Equations for Melts with Anisotropic Viscoplastic Flow

    SciTech Connect

    De Focatiis, Davide S. A.; Buckley, C. Paul; Embery, John

    2008-07-07

    This paper investigates the behaviour of a well-characterised monodisperse grade of entangled atactic polystyrene across a very wide temperature and strain rate range through linear and non-linear melt rheology and solid-state deformation. In an effort to construct a constitutive model for large deformations able to describe rheological response right across this wide timescale, two well-established rheological models are combined: the well known RoliePoly (RP) conformational melt model and the Oxford glass-rubber constitutive model for glassy polymers. Comparisons between experimental data and simulations from a numerical implementation of the model illustrate that the model can cope well with the range of deformations in which orientation is limited to length-scales longer than an entanglement length. One approach in which the model can be expanded to incorporate the effects of orientation on shorter length scales using anisotropic viscoplastic flow is briefly discussed.

  4. TiO2-SEO Block Copolymer Nanocomposites as Solid-State Electrolytes for Lithium Metal Batteries

    NASA Astrophysics Data System (ADS)

    Gurevitch, Inna; Buonsanti, Raffaella; Teran, Alexander; Cabana, Jordi; Balsara, Nitash

    2013-03-01

    Replacing the liquid electrolyte in lithium batteries by a solid has been a long-standing goal of the battery industry due to the promise of better safety and the potential to produce batteries with higher energy densities. Recently, symmetric polystyrene-block-poly(ethylene oxide) (SEO) copolymers/LiX salt mixtures with high ionic conductivity and high shear modulus were developed as solid electrolytes. For an enhancement in mechanical properties and its effect on the dendrite growth from lithium metal electrodes, we study the effect of adding TiO2 nanoparticles to the SEO/LiX mixtures. We find that TiO2/SEO/LiX nanocomposite electrolytes have stable performance against the lithium metal electrodes. There appears to be a correlation between the stability of the electrolytes, morphology, and mechanical properties.

  5. Method of synthesizing polymers from a solid electrolyte

    DOEpatents

    Skotheim, Terje A.

    1985-01-01

    A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte wherein an assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

  6. Method of synthesizing polymers from a solid electrolyte

    DOEpatents

    Skotheim, T.A.

    1984-10-19

    A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte is disclosed. An assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

  7. 2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion.

    PubMed

    Kang, Keehoon; Watanabe, Shun; Broch, Katharina; Sepe, Alessandro; Brown, Adam; Nasrallah, Iyad; Nikolka, Mark; Fei, Zhuping; Heeney, Martin; Matsumoto, Daisuke; Marumoto, Kazuhiro; Tanaka, Hisaaki; Kuroda, Shin-Ichi; Sirringhaus, Henning

    2016-08-01

    Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

  8. Hybrid electrolytes prepared from ionic liquid-grafted alumina for high-efficiency quasi-solid-state dye-sensitized solar cells.

    PubMed

    Chi, Won Seok; Roh, Dong Kyu; Kim, Sang Jin; Heo, Sung Yeon; Kim, Jong Hak

    2013-06-21

    Alumina (Al2O3) nanoparticles were covalently surface-modified with an ionic liquid (IL) to improve their miscibility with ILs such as 1-methyl-3-propylimidazolium iodide (MPII). Hybrids consisting of MPII and the surface-modified IL-Al2O3 nanoparticles were utilized as an I2-free electrolyte for quasi-solid-state dye-sensitized solar cells (DSSCs). The synthesis and properties of the IL-Al2O3 nanoparticles and hybrid electrolytes were characterized by Fourier transform infrared (FT-IR) spectroscopy, UV-visible spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The viscosity of the electrolyte continuously increased with the content of IL-Al2O3, and the fluidity almost disappeared completely when the MPII:IL-Al2O3 weight ratio was 95 : 5 or 90 : 10. The energy conversion efficiencies of DSSCs fabricated with IL-Al2O3 were always greater than those with pristine Al2O3. Such a finding is due to the favorable interactions and good miscibility between MPII and IL-Al2O3, which in turn results in the formation of an interconnected channel pathway for ion transport. Incident photon-to-electron conversion efficiency (IPCE), intensity modulated photocurrent spectroscopy (IMPS)/intensity-modulated photovoltage spectroscopy (IMVS), and electrochemical impedance spectroscopy (EIS) measurements were used to investigate the interfacial properties and electron transport characteristics. Upon utilizing double-layer structures with mesoporous TiO2 beads, the efficiency increased to 7.6% at 100 mW cm(-2), one of the highest values reported for quasi-solid-state DSSCs.

  9. Solid-state rechargeable magnesium battery

    DOEpatents

    Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

    2016-09-06

    Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

  10. Ferroelectric polymer thin films for solid-state non-volatile random access memory applications

    NASA Astrophysics Data System (ADS)

    Kaza, Swaroop

    Electronic polymers offer significant advantages towards ubiquitous computing due to their low-cost, flexibility and benign fabrication conditions. In this research, ferroelectric polymers were investigated for usage in non-volatile memory applications. The work is focused on the fabrication and ferroelectricity of Polyvinylidene-trifluoroethylene and Polyamide-11 (Nylon-11) thin films. Polyvinylidene fluoride (PVDF) and its copolymers were the first class of ferroelectric polymers discovered. Although the processes and properties of PVDF and copolymers have been extensively studied, most of the reports have been on polymers in the bulk form. This work focuses on thin films of PVDF-TrFE (75:25) copolymer fabricated by solution spin-casting. Remnant polarization, Pr, of the thin films was measured to be 6 muC/cm 2 with a coercive field, Ec, of 60 MV/m. The thin film properties are highly dependent on the temperature of crystallization and is attributed to the amount of all-trans beta-phase and crystallinity. Fatigue, defined as polarization loss with repeated switching, was studied and a model based on space charge formation was proposed as the fatigue mechanism. Space charge formation was proposed to be caused by electrochemical reaction of ions (F-) at electrodes and accumulations of detrapped ions at grain boundaries. Incorporating a F- scavenger and forming small crystallites was both observed to decrease fatigue. Nylon-11 and other odd-nylons are the only other class of polymers that have been reported to exhibit ferroelectric D-E hysteresis. The published work has almost exclusively been reported on melt-quenched and cold-drawn bulk polymers and consequently there is no literature on ferroelectricity in thin film odd-nylons. The present work developed a process for the fabrication of ferroelectric thin films of nylon-11 by spin-casting. Among the solvents tested, only a solution with m-cresol was observed to result in ferroelectricity in spun films and could

  11. An innovative polymer processing method, "solid-state shear pulverization (SSSP)": Intimate mixing, compatibilization and basic understanding of the process

    NASA Astrophysics Data System (ADS)

    Tao, Ying

    Thermodynamic and kinetic limitations inherent in conventional melt mixing limit its ability to produce finely-dispersed immiscible polymer blends and achieve compatibilization. Solid-state shear pulverization (SSSP), which relies on a modified twin screw extruder to process materials in the solid state, is designed to overcome these limitations. Repeated fragmentation and fusion steps accompanying SSSP lead to intimate mixing and compatibilization which are difficult to be achieved in conventional melt mixing. This novel process method, SSSP, has been shown for the first time to be capable of forming quasi-nanostructured polymer blends. When an 80/20 wt% polystyrene (PS)/poly (methyl methacrylate) PMMA blend is made by SSSP, the blend exhibits many irregular, minor-phase domains with length scales of ˜ 100 nm or less. However, the dispersed-phase domain size in an analogous blend made by melt mixing is one order of magnitude larger. The addition of styrene (S)/methyl methacrylate (MMA) gradient copolymer into the PS/PMMA blend during SSSP compatibilizes the blend and can largely maintain the nanostructure during high temperature annealing. Compatibilization 4 can also be achieved with the addition of block copolymer during SSSP of PS/high density polyethylene (HDPE); in particular, the addition of 5 wt% styrene/ethylene-butylene/styrene (SEBS) block copolymer to a 90/10 wt% PS/HDPE blend during SSSP yields a reduction in coarsening rate by a factor of thirty relative to a melt-mixed blend without copolymer. The understanding of the basic principles associated with SSSP has been advanced. Polymer materials accumulate, and pressure is built up in the region of bi-lobe and tri-lobe kneading disk blocks, in which repeated fragmentation and fusion steps can occur. The development of polymer blend morphology along a screw during SSSP was shown to be blend specific. The attainment during SSSP of the final microstructure in PS/poly (n-butyl methacrylate) blends and the

  12. High ion conducting polymer nanocomposite electrolytes using hybrid nanofillers.

    PubMed

    Tang, Changyu; Hackenberg, Ken; Fu, Qiang; Ajayan, Pulickel M; Ardebili, Haleh

    2012-03-14

    There is a growing shift from liquid electrolytes toward solid polymer electrolytes, in energy storage devices, due to the many advantages of the latter such as enhanced safety, flexibility, and manufacturability. The main issue with polymer electrolytes is their lower ionic conductivity compared to that of liquid electrolytes. Nanoscale fillers such as silica and alumina nanoparticles are known to enhance the ionic conductivity of polymer electrolytes. Although carbon nanotubes have been used as fillers for polymers in various applications, they have not yet been used in polymer electrolytes as they are conductive and can pose the risk of electrical shorting. In this study, we show that nanotubes can be packaged within insulating clay layers to form effective 3D nanofillers. We show that such hybrid nanofillers increase the lithium ion conductivity of PEO electrolyte by almost 2 orders of magnitude. Furthermore, significant improvement in mechanical properties were observed where only 5 wt % addition of the filler led to 160% increase in the tensile strength of the polymer. This new approach of embedding conducting-insulating hybrid nanofillers could lead to the development of a new generation of polymer nanocomposite electrolytes with high ion conductivity and improved mechanical properties. © 2012 American Chemical Society

  13. Electrochemical Stability of Model Polymer Electrolyte/Electrode Interfaces

    NASA Astrophysics Data System (ADS)

    Hallinan, Daniel; Yang, Guang

    2015-03-01

    Polymer electrolytes are promising materials for high energy density rechargeable batteries. However, typical polymer electrolytes are not electrochemically stable at the charging voltage of advanced positive electrode materials. Although not yet reported in literature, decomposition is expected to adversely affect the performance and lifetime of polymer-electrolyte-based batteries. In an attempt to better understand polymer electrolyte oxidation and design stable polymer electrolyte/positive electrode interfaces, we are studying electron transfer across model interfaces comprising gold nanoparticles and organic protecting ligands assembled into monolayer films. Gold nanoparticles provide large interfacial surface area yielding a measurable electrochemical signal. They are inert and hence non-reactive with most polymer electrolytes and lithium salts. The surface can be easily modified with ligands of different chemistry and molecular weight. In our study, poly(ethylene oxide) (PEO) will serve as the polymer electrolyte and lithium bis(trifluoromethanesulfonyl) imide salt (LiTFSI) will be the lithium salt. The effect of ligand type and molecular weight on both optical and electrical properties of the gold nanoparticle film will be presented. Finally, the electrochemical stability of the electrode/electrolyte interface and its dependence on interfacial properties will be presented.

  14. Solid electrolyte material manufacturable by polymer processing methods

    DOEpatents

    Singh, Mohit; Gur, Ilan; Eitouni, Hany Basam; Balsara, Nitash Pervez

    2012-09-18

    The present invention relates generally to electrolyte materials. According to an embodiment, the present invention provides for a solid polymer electrolyte material that is ionically conductive, mechanically robust, and can be formed into desirable shapes using conventional polymer processing methods. An exemplary polymer electrolyte material has an elastic modulus in excess of 1.times.10.sup.6 Pa at 90 degrees C. and is characterized by an ionic conductivity of at least 1.times.10.sup.-5 Scm-1 at 90 degrees C. An exemplary material can be characterized by a two domain or three domain material system. An exemplary material can include material components made of diblock polymers or triblock polymers. Many uses are contemplated for the solid polymer electrolyte materials. For example, the present invention can be applied to improve Li-based batteries by means of enabling higher energy density, better thermal and environmental stability, lower rates of self-discharge, enhanced safety, lower manufacturing costs, and novel form factors.

  15. Solid polymer electrolytes for rechargeable batteries. Final report

    SciTech Connect

    Narang, S.C.; Ventura, S.C.

    1992-02-01

    SRI International has synthesized and tested new, dimensionally stable polymer electrolytes for high energy density rechargeable lithium batteries. We have prepared semi-interpenetrating networks of sulfur-substituted polyethyleneoxide with tetmethylorthosilicate (TEOS). The in situ hydrolysis of TEOS produces a mechanically stable three-dimensional network that entangles the polymer electrolytes and makes the film dimensionally flexible and stable. With this approach, the best dimensionally stable polymer electrolyte of this type produced so far, has a room temperature lithium ion conductivity of 7.5 {times} 10{sup {minus}4} S cm{sup {minus}1}. Another type of solid polymer electrolytes, polydiacetylene-based single-ion conductors with high room temperature proton conductivity were also developed. The best conductivity of these polymers is two orders of magnitude higher than that of Nafion under comparable experimental conditions. With further appropriate chemical modification, the new polymers could be used in fuel cells.

  16. Improved electrical properties of Fe nanofiller impregnated PEO + PVP:Li+ blended polymer electrolytes for lithium battery applications

    NASA Astrophysics Data System (ADS)

    Naveen Kumar, K.; Saijyothi, K.; Kang, Misook; Ratnakaram, Y. C.; Hari Krishna, K.; Jin, Dahee; Lee, Yong Min

    2016-07-01

    Solid polymer-blended electrolyte films of polyethylene oxide (PEO) + polyvinyl pyrrolidone (PVP)/lithium perchlorate embedded with iron (Fe) nanofiller in different concentrations have been synthesized by a solution casting method. The semicrystalline nature of these polymer electrolyte films has been confirmed from their XRD profiles. Polymer complex formation and ion-polymer interactions are systematically studied by FTIR and laser Raman spectral analysis. Surface morphological studies are carried out from SEM analysis. Dispersed Fe nanofiller size evaluation study has been carried out using transmission electron microscopy (TEM). In order to evaluate the thermal stability, decomposition temperature, and thermogravimetric dynamics, we carried out the TG/DTA measurement. Upon addition of Fe nanofiller to the PEO + PVP/Li+ electrolyte system, it was found to result in the enhancement of ionic conductivity. The maximum ionic conductivity has been set up to be 1.14 × 10-4 Scm-1 at the optimized concentration of 4 wt% Fe nanofiller-embedded PEO + PVP/Li+ polymer electrolyte nanocomposite at an ambient temperature. PEO + PVP/Li+ + Fe nanofiller (4 wt%) cell exhibited better performance in terms of cell parameters. Based on the cell parameters, the 4 wt% Fe nanofiller-dispersed PEO + PVP/Li+ polymer electrolyte system could be suggested as a perspective candidate for solid-state battery applications.

  17. Electrical conductivity studies on Ammonium bromide incorporated with Zwitterionic polymer blend electrolyte for battery application

    NASA Astrophysics Data System (ADS)

    Parameswaran, V.; Nallamuthu, N.; Devendran, P.; Nagarajan, E. R.; Manikandan, A.

    2017-06-01

    Solid polymer blend electrolytes are widely studied due to their extensive applications particularly in electrochemical devices. Blending polymer makes the thermal stability, higher mechanical strength and inorganic salt provide ionic charge carrier to enhance the conductivity. In these studies, 50% polyvinyl alcohol (PVA), 50% poly (N-vinyl pyrrolidone) (PVP) and 2.5% L-Asparagine mixed with different ratio of the Ammonium bromide (NH4Br), have been synthesized using solution casting technique. The prepared PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films have been characterized by various analytical methods such as FT-IR, XRD, impedance spectroscopy, TG-DSC and scanning electron microscopy. FT-IR, XRD and TG/DSC analysis revealed the structural and thermal behavior of the complex formation between PVA/PVP/L-Asparagine/doped-NH4Br. The ionic conductivity and the dielectric properties of PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films were examined using impedance analysis. The highest ionic conductivity was found to be 2.34×10-4 S cm-1 for the m.wt. composition of 50%PVA:50%PVP:2.5%L-Asparagine:doped 0.15 g NH4Br at ambient temperature. Solid state proton battery is fabricated and the observed open circuit voltage is 1.1 V and its performance has been studied.

  18. Light-cured polymer electrolytes for safe, low-cost and sustainable sodium-ion batteries

    NASA Astrophysics Data System (ADS)

    Colò, Francesca; Bella, Federico; Nair, Jijeesh R.; Gerbaldi, Claudio

    2017-10-01

    In this work we present a very simple preparation procedure of a poly(ethylene oxide) (PEO)-based crosslinked polymer electrolyte (XPE) for application in sodium-ion batteries (NIBs). The polymer electrolyte, containing NaClO4 as Na+ source, is prepared by rapid, energy saving, solvent-free photopolymerization technique, in a single step. Thermal, mechanical, morphological and electrochemical properties of the resulting XPE are thoroughly investigated. The highly ionic conducting (>1 mS cm-1 at 25 °C) polymer electrolyte is used in a lab-scale sodium cell with nanostructured TiO2 working electrode. The obtained results in terms of ambient temperature cycling behaviour (stable specific capacity of about 250 mAh g-1 at 0.1 mA cm-2 and overall remarkable stability, for a quasi-solid state Na polymer cell, upon very long term cycling exceeding 1000 reversible cycles at 0.5 mA cm-2 corresponding to > 5000 h of continuous operation) demonstrate the promising prospects of this novel XPE to be implemented in the next-generation NIBs conceived for large-scale energy storage systems, such as those connected to photovoltaic and wind factories.

  19. Polydisperse methyl β-cyclodextrin–epichlorohydrin polymers: variable contact time 13C CP-MAS solid-state NMR characterization

    PubMed Central

    Mallard, Isabelle; Baudelet, Davy; Castiglione, Franca; Ferro, Monica; Panzeri, Walter; Ragg, Enzio

    2015-01-01

    Summary The polymerization of partially methylated β-cyclodextrin (CRYSMEB) with epichlorohydrin was carried out in the presence of a known amount of toluene as imprinting agent. Three different preparations (D1, D2 and D3) of imprinted polymers were obtained and characterized by solid-state 13C NMR spectroscopy under cross-polarization magic angle spinning (CP-MAS) conditions. The polymers were prepared by using the same synthetic conditions but with different molar ratios of imprinting agent/monomer, leading to morphologically equivalent materials but with different absorption properties. The main purpose of the work was to find a suitable spectroscopic descriptor accounting for the different imprinting process in three homogeneous polymeric networks. The polymers were characterized by studying the kinetics of the cross-polarization process. This approach is based on variable contact time CP-MAS spectra, referred to as VCP-MAS. The analysis of the VCP-MAS spectra provided two relaxation parameters: T CH (the CP time constant) and T 1ρ (the proton spin-lattice relaxation time in the rotating frame). The results and the analysis presented in the paper pointed out that T CH is sensitive to the imprinting process, showing variations related to the toluene/cyclodextrin molar ratio used for the preparation of the materials. Conversely, the observed values of T 1ρ did not show dramatic variations with the imprinting protocol, but rather confirmed that the three polymers are morphologically similar. Thus the combined use of T CH and T 1ρ can be helpful for the characterization and fine tuning of imprinted polymeric matrices. PMID:26877800

  20. Polydisperse methyl β-cyclodextrin-epichlorohydrin polymers: variable contact time (13)C CP-MAS solid-state NMR characterization.

    PubMed

    Mallard, Isabelle; Baudelet, Davy; Castiglione, Franca; Ferro, Monica; Panzeri, Walter; Ragg, Enzio; Mele, Andrea

    2015-01-01

    The polymerization of partially methylated β-cyclodextrin (CRYSMEB) with epichlorohydrin was carried out in the presence of a known amount of toluene as imprinting agent. Three different preparations (D1, D2 and D3) of imprinted polymers were obtained and characterized by solid-state (13)C NMR spectroscopy under cross-polarization magic angle spinning (CP-MAS) conditions. The polymers were prepared by using the same synthetic conditions but with different molar ratios of imprinting agent/monomer, leading to morphologically equivalent materials but with different absorption properties. The main purpose of the work was to find a suitable spectroscopic descriptor accounting for the different imprinting process in three homogeneous polymeric networks. The polymers were characterized by studying the kinetics of the cross-polarization process. This approach is based on variable contact time CP-MAS spectra, referred to as VCP-MAS. The analysis of the VCP-MAS spectra provided two relaxation parameters: T CH (the CP time constant) and T 1ρ (the proton spin-lattice relaxation time in the rotating frame). The results and the analysis presented in the paper pointed out that T CH is sensitive to the imprinting process, showing variations related to the toluene/cyclodextrin molar ratio used for the preparation of the materials. Conversely, the observed values of T 1ρ did not show dramatic variations with the imprinting protocol, but rather confirmed that the three polymers are morphologically similar. Thus the combined use of T CH and T 1ρ can be helpful for the characterization and fine tuning of imprinted polymeric matrices.

  1. Solid-state nanostructured materials from self-assembly of a globular protein-polymer diblock copolymer.

    PubMed

    Thomas, Carla S; Glassman, Matthew J; Olsen, Bradley D

    2011-07-26

    Self-assembly of three-dimensional solid-state nanostructures containing approximately 33% by weight globular protein is demonstrated using a globular protein-polymer diblock copolymer, providing a route to direct nanopatterning of proteins for use in bioelectronic and biocatalytic materials. A mutant red fluorescent protein, mCherryS131C, was prepared by incorporation of a unique cysteine residue and site-specifically conjugated to end-functionalized poly(N-isopropylacrylamide) through thiol-maleimide coupling to form a well-defined model protein-polymer block copolymer. The block copolymer was self-assembled into bulk nanostructures by solvent evaporation from concentrated solutions. Small-angle X-ray scattering and transmission electron microscopy illustrated the formation of highly disordered lamellae or hexagonally perforated lamellae depending upon the selectivity of the solvent during evaporation. Solvent annealing of bulk samples resulted in a transition toward lamellar nanostructures with mCherry packed in a bilayer configuration and a large improvement in long-range ordering. Wide-angle X-ray scattering indicated that mCherry did not crystallize within the block copolymer nanodomains and that the β-sheet spacing was not affected by self-assembly. Circular dichroism showed no change in protein secondary structure after self-assembly, while UV-vis spectroscopy indicated approximately 35% of the chromophore remained optically active.

  2. Solid-State Nanostructured Materials from Self-Assembly of a Globular Protein-Polymer Diblock Copolymer

    PubMed Central

    Thomas, Carla S.; Glassman, Matthew J.; Olsen, Bradley D.

    2014-01-01

    Self-assembly of three-dimensional solid-state nanostructures containing approximately 33% by weight globular protein is demonstrated using a globular protein-polymer diblock copolymer, providing a route to direct nanopatterning of proteins for use in bioelectronic and biocatalytic materials. A mutant red fluorescent protein, mCherryS131C, was prepared by incorporation of a unique cysteine residue and site-specifically conjugated to end-functionalized poly(N-isopropylacrylamide) through thiol-maleimide coupling to form a well-defined model protein-polymer block copolymer. The block copolymer was self-assembled into bulk nanostructures by solvent evaporation from concentrated solutions. Small-angle X-ray scattering and transmission electron microscopy illustrated the formation of highly disordered lamellae or hexagonally perforated lamellae depending upon the selectivity of the solvent during evaporation. Solvent annealing of bulk samples resulted in a transition towards lamellar nanostructures with mCherry packed in a bilayer configuration and a large improvement in long range ordering. Wide-angle X-ray scattering indicated that mCherry did not crystallize within the block copolymer nanodomains and that the β-sheet spacing was not affected by self-assembly. Circular dichroism showed no change in protein secondary structure after self-assembly, while UV-vis spectroscopy indicated approximately 35% of the chromophore remained optically active. PMID:21696135

  3. Solid Polymer Electrolyte Fuel Cell Technology Program

    NASA Technical Reports Server (NTRS)

    1980-01-01

    Work is reported on phase 5 of the Solid Polymer Electrolyte (SPE) Fuel Cell Technology Development program. The SPE fuel cell life and performance was established at temperatures, pressures, and current densities significantly higher than those previously demonstrated in sub-scale hardware. Operation of single-cell Buildup No. 1 to establish life capabilities of the full-scale hardware was continued. A multi-cell full-scale unit (Buildup No. 2) was designed, fabricated, and test evaluated laying the groundwork for the construction of a reactor stack. A reactor stack was then designed, fabricated, and successfully test-evaluated to demonstrate the readiness of SPE fuel cell technology for future space applications.

  4. Advanced composite polymer electrolyte fuel cell membranes

    SciTech Connect

    Wilson, M.S.; Zawodzinski, T.A.; Gottesfeld, S.; Kolde, J.A.; Bahar, B.

    1995-09-01

    A new type of reinforced composite perfluorinated polymer electrolyte membrane, GORE-SELECT{trademark} (W.L. Gore & Assoc.), is characterized and tested for fuel cell applications. Very thin membranes (5-20 {mu}m thick) are available. The combination of reinforcement and thinness provides high membrane, conductances (80 S/cm{sup 2} for a 12 {mu}m thick membrane at 25{degrees}C) and improved water distribution in the operating fuel cell without sacrificing longevity or durability. In contrast to nonreinforced perfluorinated membranes, the x-y dimensions of the GORE-SELECT membranes are relatively unaffected by the hydration state. This feature may be important from the viewpoints of membrane/electrode interface stability and fuel cell manufacturability.

  5. Solid-polymer-electrolyte fuel cells

    SciTech Connect

    Fuller, T.F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich`s solution and analysis.

  6. Synthesis and characterization of perovskite-type (Li,Sr)(Zr,Nb)O3 quaternary solid electrolyte for all-solid-state batteries

    NASA Astrophysics Data System (ADS)

    Yu, Ran; Du, Qing-Xia; Zou, Bang-Kun; Wen, Zhao-Yin; Chen, Chun-Hua

    2016-02-01

    Stable solid electrolytes with high lithium ionic conductivity are crucial for all-solid-state lithium ion batteries. The compatibility with electrodes require a sintering temperature around 1000 °C. A perovskite-type (Li,Sr)(Zr,Nb)O3 system with A-site vacancy is designed and synthesized by a solid-state reaction route. Four compositions with different concentrations of A-site vacancy and several sintering temperatures between 1100 and 1300 °C are selected to find an optimal composition. X-ray diffraction and scanning electron microscope are employed to analyze the crystalline phases and the microstructure of the sintered samples. The ionic conductivities of the materials are measured by AC impedance spectroscopy. For the sample with the optimal composition Li3/8Sr7/16Zr1/4Nb3/4O3 and sintered at 1200 °C, its total ionic conductivity is 2.00×10-5 and 1.65×10-4 Scm-1 at 30 and 100 °C, respectively. Its activation energy for lithium ion conduction is 0.26 eV.

  7. Solid state direct bonding of polymers by vacuum ultraviolet light below 160 nm

    NASA Astrophysics Data System (ADS)

    Hashimoto, Yuki; Yamamoto, Takatoki

    2017-10-01

    This work investigated the application of vacuum ultraviolet (VUV) irradiation to the bonding of various substrates, including glass, polycarbonate (PC), cyclic olefin polymer (COP), polydimethylsiloxane (PDMS) and polymethyl methacrylate (PMMA). This method has the advantage of being able to bond various substrates without the application of heat or adhesives, and therefore may be very useful in the fabrication of micro/nanoscale structures composed of polymers. In contrast to previous applications of this technique, the present study used VUV radiation at wavelengths at and below 160 nm so as to take advantage of the higher energy in this range. Bonding was assessed based on measuring the shear stress of various test specimens subjected to VUV irradiation and then pressed together, and a number of analytical methods were also employed to examine the irradiated surfaces in order to elucidate the morphological and chemical changes following VUV treatment. These analyses included water contact angle measurements, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), time of flight secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy (AFM). Poor bonding was identified between combinations consisting of PMMA/PC, PMMA/COP, PMMA/PMMA, PMMA/glass, and PC/COP, whereas all other combinations resulted in successful bonding with the bonding stress values such as PC/PC = 2.0 MPa, PC/glass = 10.7 MPa and COP/COP = 1.7 MPa, respectively.

  8. Energetic alignment in nontoxic SnS quantum dot-sensitized solar cell employing spiro-OMeTAD as the solid-state electrolyte

    PubMed Central

    Oda, Yoshiaki; Shen, Heping; Zhao, Lin; Li, Jianbao; Iwamoto, Mitsumasa; Lin, Hong

    2014-01-01

    An environmentally friendly solid-state quantum dot sensitized solar cell (ss-QDSSC) was prepared by combining colloidal SnS QDs as the sensitizer and organic hole scavenger spiro-OMeTAD (2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine)9,9′-spirobifluorene) as the solid-state electrolyte, and the energy alignment of SnS and TiO2 was investigated. The bandgap of colloidal SnS QDs increased with decreasing particle size from 14 to 4 nm due to an upshift of the conduction band and a downshift of the valence band. In TiO2/SnS heterojunctions, the conduction band minimum (CBM) difference between TiO2 and SnS was as large as ∼0.8 eV; this difference decreased with decreasing particle size, but was sufficient for electron injection from SnS nanoparticles of any size into TiO2. Meanwhile, the sensitizer regeneration driving force, that is, the difference between the valence band maximum (VBM) of SnS and the work function of the electrolyte, showed an opposite behaviour with the SnS size due to a downward shift of the SnS VB. Consequently, smaller SnS QDs should result in a more efficient charge transfer in heterojunctions, revealing the advantages of QDs vs larger particles as sensitizers. This prediction was confirmed by the improved photovoltaic performance of ss-QDSSCs modified with SnS nanoparticles, which peaked for 5–6 nm sized SnS nanoparticles due to the balance between electron injection and sunlight absorption. PMID:27877682

  9. Energetic alignment in nontoxic SnS quantum dot-sensitized solar cell employing spiro-OMeTAD as the solid-state electrolyte.

    PubMed

    Oda, Yoshiaki; Shen, Heping; Zhao, Lin; Li, Jianbao; Iwamoto, Mitsumasa; Lin, Hong

    2014-06-01

    An environmentally friendly solid-state quantum dot sensitized solar cell (ss-QDSSC) was prepared by combining colloidal SnS QDs as the sensitizer and organic hole scavenger spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)9,9'-spirobifluorene) as the solid-state electrolyte, and the energy alignment of SnS and TiO2 was investigated. The bandgap of colloidal SnS QDs increased with decreasing particle size from 14 to 4 nm due to an upshift of the conduction band and a downshift of the valence band. In TiO2/SnS heterojunctions, the conduction band minimum (CBM) difference between TiO2 and SnS was as large as ∼0.8 eV; this difference decreased with decreasing particle size, but was sufficient for electron injection from SnS nanoparticles of any size into TiO2. Meanwhile, the sensitizer regeneration driving force, that is, the difference between the valence band maximum (VBM) of SnS and the work function of the electrolyte, showed an opposite behaviour with the SnS size due to a downward shift of the SnS VB. Consequently, smaller SnS QDs should result in a more efficient charge transfer in heterojunctions, revealing the advantages of QDs vs larger particles as sensitizers. This prediction was confirmed by the improved photovoltaic performance of ss-QDSSCs modified with SnS nanoparticles, which peaked for 5-6 nm sized SnS nanoparticles due to the balance between electron injection and sunlight absorption.

  10. Proton Conducting Polymer Electrolyte Based on Pva-Pan

    NASA Astrophysics Data System (ADS)

    Devi, S. Siva; Selvasekarapandian, S.; Rajeswari, N.; Genova, F. Kingslin Mary; Karthikeyan, S.; Raja, C. Sanjeevi

    2013-07-01

    Proton conducting polymer electrolytes based on blend polymer using Poly Vinyl Alcohol (PVA) and Poly Acrylo Nitrile (PAN) doped with ammonium nitrate have been prepared by solution casting method. The highest conductivity at room temperature (305K) has been found to be 1.8×10-3 S cm-1 for 15 mole % NH4NO3 doped PVA-PAN system. X ray Diffraction pattern of the doped and the undoped blend polymer electrolyte confirms the amorphous nature of blend polymer, when salt is added. The complex formation between the blend polymer and the salt has been confirmed by Fourier transform infrared spectroscopy.

  11. Solid state NMR and IR characterization of wood polymer structure in relation to tree provenance.

    PubMed

    Santoni, Ilaria; Callone, Emanuela; Sandak, Anna; Sandak, Jakub; Dirè, Sandra

    2015-03-06

    (13)C nuclear magnetic resonance and mid-infrared spectroscopies were used for characterizing changes in the chemical structure of wood polymers (cellulose, hemicellulose and lignin) in relation to the tree growth location. Samples of three provenances in Europe (Finland, Poland and Italy) were selected for studies. The requirement was to use untreated solid wood samples to minimize any manipulation to the nanostructure of native wood. The results confirm that the chemical and physical properties of samples belonging to the same wood species (Picea abies Karst.) differ due to the origin. Both FT-IR and dynamic NMR spectroscopies were able to correctly discriminate samples originating from three different provenances in Europe. Such methods might be very useful for both, research and understanding of wood microstructure and its variability due to the growth conditions.

  12. Lithium Ion Polymer Electrolyte Based on Pva-Pan

    NASA Astrophysics Data System (ADS)

    Genova, F. Kingslin Mary; Selvasekarapandian, S.; Rajeswari, N.; Devi, S. Siva; Karthikeyan, S.; Raja, C. Sanjeevi

    2013-07-01

    The polymer blend electrolytes based on polyvinylalcohol(PVA) and polyacrylonitrile (PAN) doped with lithium per chlorate (LiClO4) have been prepared by solution casting technique using DMF as solvent. The complex formation between blend polymer and the salt has been confirmed by Fourier transform infrared spectroscopy. The amorphous nature of the blend polymer electrolyte has been confirmed by X-ray diffraction analysis. The ionic conductivity of the prepared blend polymer electrolyte has been found by ac impedence spectroscopic analysis. The highest ionic conductivity has been found to be 5.0 X10-4 S cm -1 at room temperature for 92.5 PVA: 7.5PAN: 20 molecular wt. % of LiClO4. The effect of salt concentration on the conductivity of the blend polymer electrolyte has been discussed.

  13. Electrospun nanocomposite fibrous polymer electrolyte for secondary lithium battery applications

    NASA Astrophysics Data System (ADS)

    Padmaraj, O.; Rao, B. Nageswara; Jena, Paramananda; Venkateswarlu, M.; Satyanarayana, N.

    2014-04-01

    Hybrid nanocomposite [poly(vinylidene fluoride -co- hexafluoropropylene) (PVdF-co-HFP)/magnesium aluminate (MgAl2O4)] fibrous polymer membranes were prepared by electrospinning method. The prepared pure and nanocomposite fibrous polymer electrolyte membranes were soaked into the liquid electrolyte 1M LiPF6 in EC: DEC (1:1,v/v). XRD and SEM are used to study the structural and morphological studies of nanocomposite electrospun fibrous polymer membranes. The nanocomposite fibrous polymer electrolyte membrane with 5 wt.% of MgAl2O4 exhibits high ionic conductivity of 2.80 × 10-3 S/cm at room temperature. The charge-discharge capacity of Li/LiCoO2 coin cells composed of the newly prepared nanocomposite [(16 wt.%) PVdF-co-HFP+(5 wt.%) MgAl2O4] fibrous polymer electrolyte membrane was also studied and compared with commercial Celgard separator.

  14. Solid state characterisation and taste masking efficiency evaluation of polymer based extrudates of isoniazid for paediatric administration.

    PubMed

    Keating, Alison V; Soto, Jessica; Tuleu, Catherine; Forbes, Claire; Zhao, Min; Craig, Duncan Q M

    2017-07-04

    Hot melt extrusion has gained considerable attention as a novel technique for taste masking of bitter APIs. The aim of this study was to investigate whether hot melt extrusion could be used to develop taste masked formulations of isoniazid and also to evaluate and correlate different taste assessment methods Two polymers with different physico-chemical properties, Soluplus and Eudragit E-PO were chosen as carriers for the drug. Eudragit E-PO has already been widely used for taste masking due to its selective release properties, while Soluplus has not been studied in this regard but provides a useful comparator of a polymer that should release the drug reasonably efficiently. Polymeric formulations of isoniazid were produced with drug loadings of 20% and 30% w/w. The solid state characteristics of the formulations were assessed by differential scanning calorimetry and powder X-ray diffraction. The taste of isoniazid was assessed using the rodent Brief Access Taste Aversion (BATA) model, while formulations were assessed using the electronic tongue and dissolution under simulated oral conditions. Investigation into the drug loading effect with these two polymers showed that all Soluplus based extrudates with drug loading up to 30% w/w were fully amorphous while Eudragit E-PO based extrudates contained crystalline drug as demonstrated by both DSC and PXRD, dependent on loading. BATA testing of isoniazid gave an IC50 value, i.e. the dose of drug which inhibits 50% of licks, of 11.1mg/mL. Taste assessment of the formulations using both simulated oral drug release and the electronic tongue demonstrated that Eudragit E-PO based formulations had a better taste masking efficiency than Soluplus. This is due to the fact that significantly less isoniazid is released from the Eudragit E-PO based formulations under oral conditions. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  15. Catalyst supports for polymer electrolyte fuel cells.

    PubMed

    Subban, Chinmayee; Zhou, Qin; Leonard, Brian; Ranjan, Chinmoy; Edvenson, Heather M; Disalvo, F J; Munie, Semeret; Hunting, Janet

    2010-07-28

    A major challenge in obtaining long-term durability in fuel cells is to discover catalyst supports that do not corrode, or corrode much more slowly than the current carbon blacks used in today's polymer electrolyte membrane fuel cells. Such materials must be sufficiently stable at low pH (acidic conditions) and high potential, in contact with the polymer membrane and under exposure to hydrogen gas and oxygen at temperatures up to perhaps 120 degrees C. Here, we report the initial discovery of a promising class of doped oxide materials for this purpose: Ti(1-x)M(x)O(2), where M=a variety of transition metals. Specifically, we show that Ti(0.7)W(0.3)O(2) is electrochemically inert over the appropriate potential range. Although the process is not yet optimized, when Pt nanoparticles are deposited on this oxide, electrochemical experiments show that hydrogen is oxidized and oxygen reduced at rates comparable to those seen using a commercial Pt on carbon black support.

  16. Reference electrodes for solid polymer electrolytes

    SciTech Connect

    Johnson, C.S.; Dees, D.W.

    1993-12-31

    Electrochemical experiments were conducted on a binary metallic lithium-tin alloy that may be suitable as a reference electrode of the first kind in studies of lithium-polymer batteries. Two types of tin electrodes were tested: bulk tin foil and tin thin films deposited on a stainless steel substrate. Electrochemical test cells were fabricated, with tin, metallic lithium, poly(ethylene oxide), and lithium trifluoromethanesulfonate as electrodes and polymer electrolyte material. To form the alloy, the tin electrodes were galvanostatically loaded in situ with lithium. Each cell reached one or more steady-state voltage plateaus during the electrochemical reduction of lithium cations at the tin electrode surface. The lithiated tin foil electrode (1 C/cm{sup 2} of charge passed; area {approx} 5 cm{sup 2}; thickness = 1.0 mm) demonstrated good voltage stability over months under open-circuit conditions. This electrode maintained an average open circuit voltage of 0.7336 V with only {plus_minus}0.17 mV variance. Composition of phases in the thin film electrodes (x in Li{sub x}Sn) was coulometrically varied via reversible lithium loading and unloading reactions. Results show that three different, two-phase compositions may be formed that maintain flat voltage regions at approximately 0.53, 0.63, and 0.73 V vs lithium metal.

  17. High Performance and Long-Term Stability in Ambiently Fabricated Segmented Solid-State Polymer Electrochromic Displays.

    PubMed

    Remmele, Julian; Shen, D Eric; Mustonen, Tero; Fruehauf, Norbert

    2015-06-10

    This work reports on the performance of a segmented polymer electrochromic display that was fabricated with solution-based processes in ambient atmosphere. An encapsulation process and the combination of structured wells for the polymer electrochrome and electrolyte layers as well as the use of a preoxidized counter polymer yields high contrasts and fast switching speeds. Asymmetric driving-with respect to time-of the display is investigated for the first time and the degradation effects in the electrochrome layer are analyzed and addressed to yield a stable device exceeding 100,000 switching cycles. A printed circuit board was integrated with the display, allowing the device to be run as a clock, where the segments only required short pulses to switch without the need for a constant current to maintain its state. Such an application pairs well with the advantages of electrochromic polymers, drawing on its high contrast, stability, and ability to maintain its colored or colorless state without the need for a constant power supply, to demonstrate the promise as well as the challenges of developing more sophisticated electrochromic devices.

  18. Hybrid Polymer/Garnet Electrolyte with a Small Interfacial Resistance for Lithium-Ion Batteries.

    PubMed

    Li, Yutao; Xu, Biyi; Xu, Henghui; Duan, Huanan; Lü, Xujie; Xin, Sen; Zhou, Weidong; Xue, Leigang; Fu, Gengtao; Manthiram, Arumugam; Goodenough, John B

    2017-01-16

    Li7 La3 Zr2 O12 -based Li-rich garnets react with water and carbon dioxide in air to form a Li-ion insulating Li2 CO3 layer on the surface of the garnet particles, which results in a large interfacial resistance for Li-ion transfer. Here, we introduce LiF to garnet Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZT) to increase the stability of the garnet electrolyte against moist air; the garnet LLZT-2 wt % LiF (LLZT-2LiF) has less Li2 CO3 on the surface and shows a small interfacial resistance with Li metal, a solid polymer electrolyte, and organic-liquid electrolytes. An all-solid-state Li/polymer/LLZT-2LiF/LiFePO4 battery has a high Coulombic efficiency and long cycle life; a Li-S cell with the LLZT-2LiF electrolyte as a separator, which blocks the polysulfide transport towards the Li-metal, also has high Coulombic efficiency and kept 93 % of its capacity after 100 cycles.

  19. Effect of TiO2 ceramic filler on PEG-based composite polymer electrolytes for magnesium batteries

    NASA Astrophysics Data System (ADS)

    Polu, Anji Reddy; Kumar, Ranveer; Kumar, K. Vijaya; Jyothi, N. Krishna

    2013-02-01

    Composite polymer electrolytes based on poly(ethylene glycol) (PEG), magnesium acetate [Mg(CH3COO)2] and x wt. % of titanium oxide (TiO2) ceramic fillers (where x = 0, 5, 10, 15 and 20 respectively) have been prepared using solution casting technique. Several experimental techniques, such as composition-dependent conductivity, temperature dependent conductivity in the temperature range of 303-333 K and transport number measurements, have been employed to characterize these composite polymer electrolyte systems. The transference number data indicated the dominance of ion-type charge transport in these specimens. Using this (PEG-Mg(CH3COO)2-TiO2) (85-15-10) electrolyte, solid state electrochemical cell was fabricated and their discharge profiles were studied under a constant load of 100 kω.

  20. Fuel cells with solid polymer electrolyte and their application on vehicles

    SciTech Connect

    Fateev, V.

    1996-04-01

    In Russia, solid polymer electrolyte MF-4-SK has been developed for fuel cells. This electrolyte is based on perfluorinated polymer with functional sulfogroups. Investigations on electrolyte properties and electrocatalysts have been carried out.

  1. Anion-controlled assembly of silver-di(aminophenyl)sulfone coordination polymers: Syntheses, crystal structures, and solid state luminescence

    SciTech Connect

    Zhang, Qi-Long; Hu, Peng; Zhao, Yi; Feng, Guang-Wei; Zhang, Yun-Qian; Zhu, Bi-Xue; Tao, Zhu

    2014-02-15

    Five silver coordination polymers, namely, ([Ag(3,3′-daps){sub 2}]·BF{sub 4}){sub n} (1), ([Ag(3,3′-daps){sub 2}]·NO{sub 3}){sub n} (2), [Ag(3,3′-daps)(CF{sub 3}SO{sub 3})]{sub n} (3), ([Ag(4,4′-daps)]·CF{sub 3}SO{sub 3}){sub n} (4), and ([Ag(4,4′-daps)]·ClO{sub 4}){sub n} (5) (3,3′-daps=di(3′-aminodiphenyl)sulfone, and 4,4′-daps=di(4′-aminodiphenyl)sulfone) have been synthesized and structural characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analyses. Complex 1 displays a 1D ladder-like chain with four-connected Ag ions and bridged 3,3′-daps. Complex 2 shows other 1D ladder chain modified by tentacles. Complex 3 is a 2D layer structure with both Ag ions and 3,3′-daps are 3-connected nodes. Complex 4 is another 1D ladder chain with three-connected Ag ions and 4,4′-daps. Complex 5 shows a 2D 4{sup 4}-sql net with Ag ions and 4,4′-daps as 4-connected nodes. Moreover, their solid state luminescence and thermal stabilities also have been investigated. - Graphical abstract: Pictogram: Synthetic procedures of the five anion controlled silver coordination polymers. We reported the synthetic procedures, structure, and luminescence property of the five anion controlled silver coordination polymers based on two novel di(aminophenyl)sulfone V-shaped ligands. Display Omitted - Highlights: • Five new silver coordination polymers were synthesized and characterized. • Two novel designed V-shaped di(aminophenyl)sulfone ligands were first introduced to coordination chemistry. • Anions play important roles in determining the five silver coordination polymers. • The structural diversity and photoluminescence property were also discussed.

  2. Polymer--Ionic liquid Electrolytes for Electrochemical Capacitors

    NASA Astrophysics Data System (ADS)

    Ketabi, Sanaz

    Polymer electrolyte, comprised of ionic conductors, polymer matrix, and additives, is one of the key components that control the performance of solid flexible electrochemical capacitors (ECs). Ionic liquids (ILs) are highly promising ionic conductors for next generation polymer electrolytes due to their excellent electrochemical and thermal stability. Fluorinated ILs are the most commonly applied in polymer-IL electrolytes. Although possessing high conductivity, these ILs have low environmental favorability. The aim of this work was to develop environmentally benign polymer-ILs for both electrochemical double layer capacitors (EDLCs) and pseudocapacitors, and to provide insights into the influence of constituent materials on the ion conduction mechanism and the structural stability of the polymer-IL electrolytes. Solid polymer electrolytes composed of poly(ethylene oxide) (PEO) and 1-ethyl-3-methylimidazolium hydrogen sulfate (EMIHSO4) were investigated for ECs. The material system was optimized to achieve the two criteria for high performance polymer-ILs: high ionic conductivity and highly amorphous structure. Thermal and structural analyses revealed that EMIHSO4 acted as an ionic conductor and a plasticizer that substantially decreased the crystallinity of PEO. Two types of inorganic nanofillers were incorporated into these polymer electrolytes. The effects of SiO2 and TiO2 nanofillers on ionic conductivity, crystallinity, and dielectric properties of PEO-EMIHSO 4 were studied over a temperature range from -10 °C and 80 °C. Using an electrochemical capacitor model, impedance (complex capacitance) and dielectric analyses were performed to understand the ionic conduction process with and without fillers in both semi crystalline and amorphous states of the polymer electrolytes. Despite their different nanostructures, both SiO2 and TiO2 promoted an amorphous structure in PEO-EMIHSO 4 and increased the ionic conductivity 2-fold. While in the amorphous state, the

  3. An integrated approach for structural characterization of complex solid state electrolytes: the case of lithium lanthanum titanate

    SciTech Connect

    Cheng, Y. Q.; Bi, Z. H.; Huq, A.; Feygenson, M.; Bridges, C. A.; Paranthaman, M. P.; Sumpter, B. G.

    2014-01-08

    For neutron scattering and first principles simulation we integrate them to reveal the atomic-level to nanoscale structure of lithium lanthanum titanate (LLTO), a representative solid electrolyte material with applications in Li-ion batteries. Furthermore, the integrated approach solves the hierarchical local structure of LLTO in detail, including the coupled chemical order and topological distortion, as well as their correlation length scale and the spatial modulation with coherent boundaries. Ab initio molecular dynamics simulations are used to map out the distribution of the mobile ions and identify the migration pathway. This integrated approach provides a powerful means for detailed study of materials with complex local chemical and topological environment.

  4. Cation Mixing Properties toward Co Diffusion at the LiCoO2 Cathode/Sulfide Electrolyte Interface in a Solid-State Battery.

    PubMed

    Haruyama, Jun; Sodeyama, Keitaro; Tateyama, Yoshitaka

    2017-01-11

    All-solid-state Li-ion batteries (ASS-LIBs) are expected to be the next-generation battery, however, their large interfacial resistance hinders their widespread application. To understand and resolve the possible causes of this resistance, we examined mutual diffusion properties of the cation elements at LiCoO2 (LCO) cathode/β-Li3PS4 (LPS) solid electrolyte interface as a representative system as well as the effect of a LiNbO3 buffer layer by first-principles calculations. Evaluating energies of exchanging ions between the cathode and the electrolyte, we found that the mixing of Co and P is energetically preferable to the unmixed states at the LCO/LPS interface. We also demonstrated that the interposition of the buffer layer suppresses such mixing because the exchange of Co and Nb is energetically unfavorable. Detailed analyses of the defect levels and the exchange energies by using the individual bulk crystals as well as the interfaces suggest that the lower interfacial states in the energy gap can make a major contribution to the stabilization of the Co ↔ P exchange, although the anion bonding preference of Co and P as well as the electrostatic interactions may have effects as well. Finally, the Co ↔ P exchanges induce interfacial Li sites with low chemical potentials, which enhance the growth of the Li depletion layer. These atomistic understandings can be meaningful for the development of ASS-LIBs with smaller interfacial resistances.

  5. All solid-state electrochemical capacitors using N,N-dimethylpyrrolidinium fluorohydrogenate as ionic plastic crystal electrolyte

    NASA Astrophysics Data System (ADS)

    Taniki, Ryosuke; Matsumoto, Kazuhiko; Nohira, Toshiyuki; Hagiwara, Rika

    2014-01-01

    An electrochemical capacitor using an ionic plastic crystal of N,N-dimethylpyrrolidinium fluorohydrogenate (DMPyr(FH)2F) as a solid electrolyte has been successfully operated with activated carbon electrodes at 298 K. Typical square-shapes for electric double-layer capacitors are observed in the cyclic voltammogram within the narrow potential regions. In the wide potential regions, the redox reactions involving fluorohydrogenate anions occur on both the positive and negative electrodes. The galvanostatic charge-discharge test confirms stable operation of the electrochemical capacitor using the present ionic plastic crystal. The capacitances of the positive and negative electrodes are 263 and 221 F g-1 (capacitance per gram of electrode weight), respectively, at the 300th cycle when the cell is charged up to the voltage of 2.5 V with a current density of 238 mA g-1. The ac impedance test shows that ions in the ionic plastic crystal form double-layer between electrolyte and internal surface of the pore of activated carbon. The open-circuit voltage decreases proportionally to the square root of time within the first 10 s after galvanostatic charging, which confirms that the ions inhomogeneously distributed in the pore of activated carbon migrate to be homogeneous under a diffusion-limited process.

  6. Solid-state structure of gelatin-mono epoxy terminated polydimethylsiloxane polymer: effect of electrostatic and hydrophobic interactions.

    PubMed

    Xu, Jing; Xia, Yongmei; Qiao, Cong-De; Zhu, Weiyue; Wang, Yuexia; Li, Tian-Duo

    2014-11-01

    In this study, a hybrid synthetic gelatin-mono epoxy terminated polydimethylsiloxane polymer (PDMS-E grafted gelatin (PGG)) was successfully synthesized on a large scale. Supramolecular structure of gelatin, which was decided by the sophisticated inter- and intra-molecular interactions, significantly affected the self-assembly and phase behavior of PGG. Interestingly, the supramolecular organization of PGG could be tuned finely by negatively charged surfactants, such as sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfonate (STSo), as revealed by high-resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), light microscopy (LM), and atomic force microscopy (AFM). SEM images exhibited the presence of spherical aggregates in PGG/SDS films while hexagonal array was observed in PGG/STSo films. The results of LM revealed that when PGG/STSo solution was dried, a successive structural transformation from spheres to hexagons, via sticks and butterfly-shaped aggregates as intermediates, was observed. However, the morphologies of the aggregates formed in PGG/SDS system did not exhibit any obvious change upon drying. Attenuated total reflection-Fourier transform infrared spectra combined with AFM observations indicated that the secondary structure and aggregation behavior of gelatin was modified with the change in the electrostatic and hydrophobic interactions, leading to the formation of diversified solid-state structures of PGG.

  7. Norbornene-Based Polymer Electrolytes for Lithium Cells

    NASA Technical Reports Server (NTRS)

    Cheung, Iris; Smart, Marshall; Prakash, Surya; Miyazawa, Akira; Hu, Jinbo

    2007-01-01

    Norbornene-based polymers have shown promise as solid electrolytes for lithium-based rechargeable electrochemical cells. These polymers are characterized as single-ion conductors. Single-ion-conducting polymers that can be used in lithium cells have long been sought. Single-ion conductors are preferred to multiple-ion conductors as solid electrolytes because concentration gradients associated with multiple-ion conduction lead to concentration polarization. By minimizing concentration polarization, one can enhance charge and discharge rates. Norbornene sulfonic acid esters have been synthesized by a ring-opening metathesis polymerization technique, using ruthenium-based catalysts. The resulting polymer structures (see figure) include sulfonate ionomers attached to the backbones of the polymer molecules. These molecules are single-ion conductors in that they conduct mobile Li+ ions only; the SO3 anions in these polymers, being tethered to the backbones, do not contribute to ionic conduction. This molecular system is especially attractive in that it is highly amenable to modification through functionalization of the backbone or copolymerization with various monomers. Polymers of this type have been blended with poly(ethylene oxide) to lend mechanical integrity to free-standing films, and the films have been fabricated into solid polymer electrolytes. These electrolytes have been demonstrated to exhibit conductivity of 2 10(exp -5)S/cm (which is high, relative to the conductivities of other solid electrolytes) at ambient temperature, plus acceptably high stability. This type of norbornene-based polymeric solid electrolyte is in the early stages of development. Inasmuch as the method of synthesis of these polymers is inherently flexible and techniques for the fabrication of the polymers into solid electrolytes are amenable to optimization, there is reason to anticipate further improvements.

  8. Poly(arylene)-based anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Bae, Chulsung

    2015-06-09

    Poly(arylene) electrolytes including copolymers lacking ether groups in the polymer may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  9. Polymer electrolytes for a rechargeable li-Ion battery

    SciTech Connect

    Argade, S.D.; Saraswat, A.K.; Rao, B.M.L.; Lee, H.S.; Xiang, C.L.; McBreen, J.

    1996-10-01

    Lithium-ion polymer electrolyte battery technology is attractive for many consumer and military applications. A Li{sub x}C/Li{sub y}Mn{sub 2}O{sub 4} battery system incorporating a polymer electrolyte separator base on novel Li-imide salts is being developed under sponsorship of US Army Research Laboratory (Fort Monmouth NJ). This paper reports on work currently in progress on synthesis of Li-imide salts, polymer electrolyte films incorporating these salts, and development of electrodes and cells. A number of Li salts have been synthesized and characterized. These salts appear to have good voltaic stability. PVDF polymer gel electrolytes based on these salts have exhibited conductivities in the range 10{sup -4} to 10{sub -3} S/cm.

  10. PVC-PBMA nanocomposite polymer electrolytes for lithium battery applications

    NASA Astrophysics Data System (ADS)

    Arunkumar, R.; Rani, M. Usha; Babu, Ravishanker

    2017-05-01

    Polyvinyl chloride (PVC)-Poly (butyl methacrylate) (PBMA) composite polymer electrolytes with incorporation of different ratio of ZrO2 doped was prepared by solution casting technique. The ionic conductivity, dielectric behavior, ionic transference number and surface morphology of the composite polymer electrolytes were characterized by using ac impedance, dielectric, DC polarization method and SEM studies respectively. The best room temperature ionic conductivity (0.520mScm-1 at 303 K), high dielectric constant (27340 ± 10 at 50 Hz) and high pore size obtained for 10 wt% of ZrO2 doped composite polymer electrolytes. DC polarization method confirms the occurrences of conduction in composite PVC-PBMA blend polymer electrolytes predominantly due to ions.

  11. Advanced Proton Conducting Polymer Electrolytes for Electrochemical Capacitors

    NASA Astrophysics Data System (ADS)

    Gao, Han

    Research on solid electrochemical energy storage devices aims to provide high performance, low cost, and safe operation solutions for emerging applications from flexible consumer electronics to microelectronics. Polymer electrolytes, minimizing device sealing and liquid electrolyte leakage, are key enablers for these next-generation technologies. In this thesis, a novel proton-conducing polymer electrolyte system has been developed using heteropolyacids (HPAs) and polyvinyl alcohol for electrochemical capacitors. A thorough understanding of proton conduction mechanisms of HPAs together with the interactions among HPAs, additives, and polymer framework has been developed. Structure and chemical bonding of the electrolytes have been studied extensively to identify and elucidate key attributes affecting the electrolyte properties. Numerical models describing the proton conduction mechanism have been applied to differentiate those attributes. The performance optimization of the polymer electrolytes through additives, polymer structural modifications, and synthesis of alternative HPAs has achieved several important milestones, including: (a) high proton mobility and proton density; (b) good ion accessibility at electrode/electrolyte interface; (c) wide electrochemical stability window; and (d) good environmental stability. Specifically, high proton mobility has been addressed by cross-linking the polymer framework to improve the water storage capability at normal-to-high humidity conditions (e.g. 50-80% RH) as well as by incorporating nano-fillers to enhance the water retention at normal humidity levels (e.g. 30-60% RH). High proton density has been reached by utilizing additional proton donors (i.e. acidic plasticizers) and by developing different HPAs. Good ion accessibility has been achieved through addition of plasticizers. Electrochemical stability window of the electrolyte system has also been investigated and expanded by utilizing HPAs with different heteroatoms

  12. Computer Simulations of Ion Transport in Polymer Electrolyte Membranes.

    PubMed

    Mogurampelly, Santosh; Borodin, Oleg; Ganesan, Venkat

    2016-06-07

    Understanding the mechanisms and optimizing ion transport in polymer membranes have been the subject of active research for more than three decades. We present an overview of the progress and challenges involved with the modeling and simulation aspects of the ion transport properties of polymer membranes. We are concerned mainly with atomistic and coarser level simulation studies and discuss some salient work in the context of pure binary and single ion conducting polymer electrolytes, polymer nanocomposites, block copolymers, and ionic liquid-based hybrid electrolytes. We conclude with an outlook highlighting future directions.

  13. Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

    PubMed

    Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

    2015-03-28

    Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

  14. Solid-state structural transformations and photoreactivity of 1D-ladder coordination polymers of Pb(II).

    PubMed

    Kole, Goutam Kumar; Peedikakkal, Abdul Malik Puthan; Toh, Belinda Mei Fang; Vittal, Jagadese J

    2013-03-18

    An attempt has been made to design double-stranded ladder-like coordination polymers (CPs) of hemidirected Pb(II) . Four CPs, [Pb(μ-bpe)(O2 C-C6 H5 )2 ]⋅2H2 O (1), [Pb2 (μ-bpe)2 (μ-O2 C-C6 H5 )2 (O2 C-C6 H5 )2 ] (2), [Pb2 (μ-bpe)2 (μ-O2 C-p-Tol)2 (O2 C-p-Tol)2 ]⋅ 1.5 H2 O (3) and [Pb2 (μ-bpe)2 (μ-O2 C-m-Tol)2 (O2 C-m-Tol)2 ] (4) (bpe=1,2-bis(4'-pyridyl)ethylene), have been synthesised and investigated for their solid-state photoreactivity. CPs 2-4, having a parallel orientation of bpe molecules in their ladder structures and being bridged by carboxylates, were found to be photoreactive, whereas CP 1 is a linear one-dimensional (1D) CP with guest water molecules aggregating to form a hydrogen-bonded 1D structure. The linear strands of 1 were found to pair up upon eliminating lattice water molecules by heating, which led to the solid-state structural transformation of photostable linear 1D CP 1 into photoreactive ladder CP 2. In the construction of the double-stranded ladder-like structures, the parallel alignment of CC bonds in 2-4 is dictated by the chelating and μ2 -η(2) :η(1) bridging modes of the benzoate and toluate ligands. The role of solvents in the formation of such double-stranded ladder-like structures has also been investigated. A single-crystal-to-single-crystal transformation occurred when 4 was irradiated under UV light to form [Pb2 (rctt-tpcb)(μ-O2 C-m-Tol)2 (O2 C-m-Tol)2 ] (5). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Hot pressed K+ ion conducting solid polymer electrolytes: synthesis, ion conduction and polymeric battery fabrication

    NASA Astrophysics Data System (ADS)

    Chandra, Angesh

    2016-07-01

    Synthesis and ion transport studies of hot pressed K+ ion conducting solid polymer electrolytes (SPEs): (1 - x) PEO: x KBr, where 0 < x < 50 in wt%, are reported. The solvent-free/hot-press method is used for synthesis of the present SPEs. The two orders of conductivity enhancement achieved after the polymer-salt complexation in SPE composition: (70:30) with conductivity ( σ) 5.01 × 10-7 S cm-1 from the room temperature conductivity measurements. Materials characterization and polymer-salt complexations of present SPEs have been explained with the help of various techniques viz. X-ray diffraction, Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy technique. To explain the ion conduction in the present SPEs, temperature dependent ionic conductivity ( σ), ionic mobility ( μ), mobile ion concentration ( n), ionic transference number ( t ion ) and ionic drift velocity ( v d ) have been calculated with the help of various experimental techniques. A solid state polymer battery is also fabricated by using the present SPE as an electrolyte and have been calculated their important cell parameters at room temperature.

  16. Polymer electrolyte fuel cells for transportation applications

    NASA Astrophysics Data System (ADS)

    Springer, T. E.; Wilson, M. S.; Garzon, F. H.; Zawodzinski, T. A.; Gottesfeld, S.

    The application of the polymer electrolyte fuel cell (PEFC) as a primary power source in electric vehicles has received increasing attention during the last few years. This increased attention has been fueled by a combination of significant technical advances in this field and by the initiation of some projects for the demonstration of a complete, PEFC-based power system in a bus or in a passenger car. Such demonstration projects reflect an increased faith of industry in the potential of this technology for transportation applications, or, at least, in the need for a detailed evaluation of this potential. Nevertheless, large scale transportation applications of PEFC's require a continued concerted effort of research on catalysis, materials and components, combined with the engineering efforts addressing the complete power system. This is required to achieve cost effective, highly performing PEFC stack and power system. We describe in this contribution some recent results of work performed within the Core Research PEFC Program at Los Alamos National Laboratory, which has addressed transportation applications of PEFC's.

  17. Experimental aspects of solid-state voltammetry

    SciTech Connect

    Wooster, T.T.; Longmire, M.L.; Zhang, H.

    1992-05-15

    This paper describes the properties of poly(ether) polymer electrolytes as solvent media for solid-state voltammetry. Experimental requirements for microelectrode voltammetry and results for the dependency of diffusive transport of electroactive solutes on polymer solvent molecular weight, structure, and temperature (and related phase state) are described for eight poly(ether)s: linear poly(ethylene oxides) MW = 400, 1000, 2000, and 600 000 (Me{sub 2}PEG-400, Me{sub 2}PEG-1000, Me{sub 2}PEG-2000, PEO-600 000), linear poly(propylene oxide) MW = 4000 (PPO-4000), the comb polymer poly(bis[(methoxyethoxy)ethoxy]phosphazine) (MEEP), the block copolymer poly(ether)-poly(urethane urea)(PEUU), and the cross-linked poly(ether) network PEO. 28 refs., 10 figs., 1 tab.

  18. Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing

    PubMed Central

    Prabhakaran, Venkateshkumar; Mehdi, B. Layla; Ditto, Jeffrey J.; Engelhard, Mark H.; Wang, Bingbing; Gunaratne, K. Don D.; Johnson, David C.; Browning, Nigel D.; Johnson, Grant E.; Laskin, Julia

    2016-01-01

    The rational design of improved electrode–electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly dispersed discrete redox-active cluster anions (50 ng of pure ∼0.75 nm size molybdenum polyoxometalate (POM) anions on 25 μg (∼0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft landing (SL). Electron microscopy provides atomically resolved images of a uniform distribution of individual POM species soft landed directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage. PMID:27097686

  19. Rational design of efficient electrode-electrolyte interfaces for solid-state energy storage using ion soft landing

    NASA Astrophysics Data System (ADS)

    Prabhakaran, Venkateshkumar; Mehdi, B. Layla; Ditto, Jeffrey J.; Engelhard, Mark H.; Wang, Bingbing; Gunaratne, K. Don D.; Johnson, David C.; Browning, Nigel D.; Johnson, Grant E.; Laskin, Julia

    2016-04-01

    The rational design of improved electrode-electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly dispersed discrete redox-active cluster anions (50 ng of pure ~0.75 nm size molybdenum polyoxometalate (POM) anions on 25 μg (~0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft landing (SL). Electron microscopy provides atomically resolved images of a uniform distribution of individual POM species soft landed directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.

  20. Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing

    DOE PAGES

    Prabhakaran, Venkateshkumar; Mehdi, B. Layla; Ditto, Jeffrey J.; ...

    2016-04-21

    Here, the rational design of improved electrode-electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly-dispersed discrete redox-active cluster anions (50 ng of pure ~0.7 nm size molybdenum polyoxometalate anions (POM) anions on 25 mg (≈ 0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft-landingmore » (SL). For the first time, electron microscopy provides atomically-resolved images of individual POM species directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.« less

  1. Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing

    SciTech Connect

    Prabhakaran, Venkateshkumar; Mehdi, B. Layla; Ditto, Jeffrey J.; Engelhard, Mark H.; Wang, Bingbing; Gunaratne, K. Don D.; Johnson, David C.; Browning, Nigel D.; Johnson, Grant E.; Laskin, Julia

    2016-04-21

    Here, the rational design of improved electrode-electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly-dispersed discrete redox-active cluster anions (50 ng of pure ~0.7 nm size molybdenum polyoxometalate anions (POM) anions on 25 mg (≈ 0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft-landing (SL). For the first time, electron microscopy provides atomically-resolved images of individual POM species directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.

  2. Novel solid state proton-conductors based on polymeric non-oxy acids. Final report

    SciTech Connect

    Appleby, A.J.; Srinivasan, S.; Parthasarathy, A.; Gonzalez, E.R.; DesMarteau, D.; Gillette, M.S.; Ghosh, J.K.; Jalan, V.; Desai, M.

    1992-01-01

    Objectives of this project were to prepare and characterize novel solid state proton-conductors and to evaluate these compounds as fuel cell electrolytes. The thrust was on the synthesis of new proton-conducting ``model`` and ``polymeric`` compounds, based on acid functions of the type (R{sub f}SO{sub 2}){sub 2}NH and (R{sub f}SO{sub 2}){sub 2}CH{sub 2} in appropriate fluorinated carbon structures, their physics-chemical characterization (Infra-red, Nuclear Magnetic Resonance, Differential Scanning Calorimetry, and X-ray Diffraction), and is pro. evaluation as candidate fuel cell electrolytes for use at elevated temperatures. This project consisted of four tasks (i) Synthesis of Proton-Conducting Polymer Electrolytes; (ii) Physical and Chemical Characterization of Proton-Conducting Polymer Electrolytes; (iii) Electrochemical Characterization of Proton-Conducting Polymer Electrolytes; and (iv) Evaluation of Proton-Conducting Polymer Electrolytes for Fuel Cells.

  3. Methacrylate based gel polymer electrolyte for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Isken, P.; Winter, M.; Passerini, S.; Lex-Balducci, A.

    2013-03-01

    A methacrylate based gel polymer electrolyte (GPE) was prepared and electrochemically investigated. The polymer was synthesized as a statistical co-polymer of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and benzyl methacrylate (BnMA) by free radical polymerization. The ethylene glycol side chain of OEGMA should be able to interact with the liquid electrolyte, thus keeping it inside the GPE, whereas BnMA was used to enhance the mechanical stability of the GPE. Such a polymer was able to retain liquid electrolyte up to 400% of its own weight, while the mechanical stability of the GPE was still high enough to be used as separator in lithium-ion batteries. The GPE displayed a conductivity of 1.8 mS cm-1 at 25 °C and an electrochemical stability window comparable to that of a standard liquid electrolyte. When used in lithium-ion batteries, such a GPE allowed a performance comparable to that obtained using conventional liquid electrolytes. Therefore the reported electrolyte was identified as a promising candidate as electrolyte for lithium-ion batteries.

  4. Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations.

    PubMed

    Sun, Bing; Mindemark, Jonas; Morozov, Evgeny V; Costa, Luciano T; Bergman, Martin; Johansson, Patrik; Fang, Yuan; Furó, István; Brandell, Daniel

    2016-04-14

    Among the alternative host materials for solid polymer electrolytes (SPEs), polycarbonates have recently shown promising functionality in all-solid-state lithium batteries from ambient to elevated temperatures. While the computational and experimental investigations of ion conduction in conventional polyethers have been extensive, the ion transport in polycarbonates has been much less studied. The present work investigates the ionic transport behavior in SPEs based on poly(trimethylene carbonate) (PTMC) and its co-polymer with ε-caprolactone (CL) via both experimental and computational approaches. FTIR spectra indicated a preferential local coordination between Li(+) and ester carbonyl oxygen atoms in the P(TMC20CL80) co-polymer SPE. Diffusion NMR revealed that the co-polymer SPE also displays higher ion mobilities than PTMC. For both systems, locally oriented polymer domains, a few hundred nanometers in size and with limited connections between them, were inferred from the NMR spin relaxation and diffusion data. Potentiostatic polarization experiments revealed notably higher cationic transference numbers in the polycarbonate based SPEs as compared to conventional polyether based SPEs. In addition, MD simulations provided atomic-scale insight into the structure-dynamics properties, including confirmation of a preferential Li(+)-carbonyl oxygen atom coordination, with a preference in coordination to the ester based monomers. A coupling of the Li-ion dynamics to the polymer chain dynamics was indicated by both simulations and experiments.

  5. Ion conducting polymers as solid electrolytes. Final report, 1985-1986

    SciTech Connect

    Semancik, J.D.

    1986-05-28

    Electrically conducting polymers have recently been the subject of much interest. In particular, their potential as electrolytes in solid-state batteries has gained the attention of the U.S. Navy. Current ion-conducting polymers have conductivities too low by a factor of ten at operational temperatures. In order to be able to obtain suitable conductivities in these polymers, a thorough understanding of the mechanisms governing ion motion in them must be attained. The processes involved in the ion conduction of one particular polymer, poly(propylene oxide) or PPO, were studied in this research. Samples were prepared using an ion-implantation procedure developed as part of the project as well as by the traditional chemical complexing technique involving alkali-metal salt doping. The samples produced were analyzed using both differential scanning calorimetry and audio-frequency complex impedance measurements. Results indicate that the polarity of the salts has a major effect upon the activation volume and the glass transition of PPO. As a result of these effects, it seems that nonpolar anions may aid in increasing the cationic transport number of the polymer. More importantly, the first direct numerical evidence of a connection between the large-scale segmental motions of the polymer chains and the chains and the conductivity has been established.

  6. Tungsten oxide-Prussian blue electrochromic system based on a proton-conducting polymer electrolyte

    SciTech Connect

    Ho, K.C.; Rukavina, T.G.; Greenberg, C.B. . Glass Technology Center)

    1994-08-01

    A new solid-state electrochromic system is presented. It is transparent and is comprised of a tungsten oxide and Prussian blue (PB) thin film couple in combination with a proton-conducting, solid polymer electrolyte. This electrochromic system exhibits rapid and deep optical switching; characteristics of a complementary configuration, both electrochromic films color and bleach in phase. Complementary electrochromic cells with the tungsten oxide-PB couple have previously been based on Li[sup +] or K[sup +]-conducting electrolytes. A repetitively cycling cell has not previously been reported with a proton-conducting solid polymer electrolyte. The devices were operated at low applied voltages, +1.2 V to darken and [minus]0.6 V to bleach. Repeated reduction and oxidation of the current system over 20,000 cycles has been demonstrated, indicating a large number of switchings without great degradation or irreversible side reactions. The sustained, high overall coloration efficiency of the devices suggests the insertion/extraction of protons into and out of both WO[sub 3] and PB films. The effects of cell size and operating temperature on the switching response are discussed.

  7. Infiltration of polymer hole-conductor into mesoporous titania structures for solid-state dye-sensitized solar cells.

    PubMed

    Rawolle, Monika; Sarkar, Kuhu; Niedermeier, Martin A; Schindler, Markus; Lellig, Philipp; Gutmann, Jochen S; Moulin, Jean-François; Haese-Seiller, Martin; Wochnik, Angela S; Scheu, Christina; Müller-Buschbaum, Peter

    2013-02-01

    The degree of filling of titania nanostructures with a solid hole-conducting material is important for the performance of solid-state dye-sensitized solar cells (ssDSSCs). Different ways to infiltrate the hole-conducting polymer poly(3-hexylthiophene) (P3HT) into titania structures, both granular structures as they are already applied commercially and tailored sponge nanostructures, are investigated. The solar cell performance is compared to the morphology determined with scanning electron microscopy (SEM) and time-of-flight grazing incidence small-angle neutron scattering (TOF-GISANS). The granular titania structure, commonly used for ssDSSCs, shows a large distribution of particle and pore sizes, with porosities in the range from 41 to 67%, including even dense parts without pores. In contrast, the tailored sponge nanostructure has well-defined pore sizes of 25 nm with an all-over porosity of 54%. Filling of the titania structures with P3HT by solution casting results in a mesoscopic P3HT overlayer and consequently a bad solar cell performance, even though a filling ratio of 67% is observed. For the infiltration by repeated spin coating, only 57% pore filling is achieved, whereas filling by soaking in the solvent with subsequent spin coating yields filling as high as 84% in the case of the tailored titania sponge structures. The granular titania structure is filled less completely than the well-defined porous structures. The solar cell performance is increased with an increasing filling ratio for these two ways of infiltration. Therefore, filling by soaking in the solvent with subsequent spin coating is proposed.

  8. Solid polymer electrolyte composite membrane comprising plasma etched porous support

    DOEpatents

    Liu, Han; LaConti, Anthony B.

    2010-10-05

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 0.1 to 5 microns, are made by plasma etching and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

  9. Infiltration of Solution-Processable Solid Electrolytes into Conventional Li-Ion-Battery Electrodes for All-Solid-State Li-Ion Batteries.

    PubMed

    Kim, Dong Hyeon; Oh, Dae Yang; Park, Kern Ho; Choi, Young Eun; Nam, Young Jin; Lee, Han Ah; Lee, Sang-Min; Jung, Yoon Seok

    2017-04-05

    Bulk-type all-solid-state lithium-ion batteries (ASLBs) have the potential to be superior to conventional lithium-ion batteries (LIBs) in terms of safety and energy density. Sulfide SE materials are key to the development of bulk-type ASLBs because of their high ionic conductivity (max of ∼10(-2) S cm(-1)) and deformability. However, the severe reactivity of sulfide materials toward common polar solvents and the particulate nature of these electrolytes pose serious complications for the wet-slurry process used to fabricate ASLB electrodes, such as the availability of solvent and polymeric binders and the formation of ionic contacts and networks. In this work, we report a new scalable fabrication protocol for ASLB electrodes using conventional composite LIB electrodes and homogeneous SE solutions (Li6PS5Cl (LPSCl) in ethanol or 0.4LiI-0.6Li4SnS4 in methanol). The liquefied LPSCl is infiltrated into the tortuous porous structures of LIB electrodes and solidified, providing intimate ionic contacts and favorable ionic percolation. The LPSCl-infiltrated LiCoO2 and graphite electrodes show high reversible capacities (141 and 364 mA h g(-1)) at 0.14 mA cm(-2) (0.1 C) and 30 °C, which are not only superior to those for conventional dry-mixed and slurry-mixed ASLB electrodes but also comparable to those for liquid electrolyte cells. Good electrochemical performance of ASLBs employing the LPSCl-infiltrated LiCoO2 and graphite electrodes at 100 °C is also presented, highlighting the excellent thermal stability and safety of ASLBs.

  10. A plasticized polymer-electrolyte-based photoelectrochemical solar cell

    SciTech Connect

    Mao, D.; Ibrahim, M.A.; Frank, A.J.

    1998-01-01

    A photoelectrochemical solar cell based on an n-GaAs/polymer-redox-electrolyte junction is reported. Di(ethylene glycol) ethyl ether acrylate containing ferrocene as a redox species and benzoin methyl ether as a photoinitiator is polymerized in situ. Propylene carbonate is used as a plasticizer to improve the conductivity of the polymer redox electrolyte. For thin (1 {micro}m) polymer electrolytes, the series resistance of the cell is negligible. However, the short-circuit photocurrent density of the cell at light intensities above 10 mW/cm{sup 2} is limited by mass transport of redox species within the polymer matrix. At a light intensity of 70 mW/cm{sup 2}, a moderate light-to-electrical energy conversion efficiency (3.1%) is obtained. The interfacial charge-transfer properties of the cell in the dark and under illumination are studied.

  11. Functional titanium oxide nano-particles as electron lifetime, electrical conductance enhancer, and long-term performance booster in quasi-solid-state electrolyte for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Lue, Shingjiang Jessie; Wu, Yun-Ling; Tung, Yung-Liang; Shih, Chao-Ming; Wang, Yi-Chun; Li, Jun-Ruei

    2015-01-01

    This research investigates the design of a quasi-solid-state electrolyte for improving the photovoltaic efficiency and long-term performance stability of dye-sensitized solar cells (DSSCs). In this study, agarose gel and titanium oxide (TiO2) nano-particles are incorporated into an iodine/iodide electrolyte solution in a 1-methyl-2-pyrrolidinone (NMP)/3-methoxypropionitrile (MPN) solvent mixture to fabricate quasi-solid-state electrolytes for 2.0-cm2 DSSCs. The electrolyte also contains an ionic liquid, 1-methyl-3-propylimidazolium iodide, and a co-additive, 1-methylbenzimidazole. The negatively charged TiO2 nano-particles exhibit an anatase crystal structure. Without agarose and TiO2, the control cell's photovoltaic efficiency drops by more than 50% over 2400 h of aging due to a significant decrease in the short-circuit current. Incorporating 1% agarose into the electrolyte not only enhances the retention of the solvent but also maintains the short-circuit current. Furthermore, adding 0.5% TiO2 to 1% agarose electrolyte provides sufficient ion and electron transfer routes and improves the fill factor of the corresponding DSSC. The photoconversion efficiency of the agarose/TiO2-containing DSSC monotonically increases from an initial value of 5.08% to 6.48% within 2400 h. The improved cell efficiency is correlated to the longer electron lifetime in the DSSC, higher ion diffusivity, and the smaller electrical resistance of the electrolyte.

  12. Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

    2017-06-22

    Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm(-1) ) and dry-air-stable SEs (Li4 SnS4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO2 ) coated by solidified Li4 SnS4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO2 to aqueous solutions are minimized by using predissolved Li4 SnS4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Electrochemical intercalation of lithium into carbons using a solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Choquette, Y.; Guerfi, A.; Simoneau, M.; Bélanger, A.; Gauthier, M.

    A study of the electrochemical performance of carbon materials from different types was carried out on true solid polymer-based poly(ethylene oxide) (PEO) with LiTFSI for application as the negative electrode in lithium ion solid-state batteries (LISSBs) at 60 °C. The reversible and irreversible capacity depend strongly on the crystallinity, the form of carbon and the impurities. A comparison of particle versus fiber was done when we investigated the charge/discharge characteristics with different current densities. The galvanostatic curves show high reversibility of the lithium—carbon in solid polymer electrolyte. The kinetics of electrochemical intercalation of lithium into carbon was studied by impedance spectroscopy especially for evaluating the diffusion coefficient in different origins of carbon. The degree of ionization of lithium was investigated by using solid-state 7Li nuclear magnetic resonance spectroscopy when the electrode is fully intercalated or doped down to 0 V. The chemical shift of 7Li NMR in lithium intercalation or doping in the carbons was classified in two ranges, 42 ppm and 9 ppm. 7Li NMR suggests the carbon with a 42 ppm range is the best choice for LISSBs.

  14. Ionic conductivity and battery characteristic studies of a new PAN-based Na+ ion conducting gel polymer electrolyte system

    NASA Astrophysics Data System (ADS)

    Krishna Jyothi, N.; Vijaya Kumar, K.; Sunita Sundari, G.; Narayana Murthy, P.

    2016-03-01

    Sodium ion conducting gel polymer electrolytes based on polyacrylonitrile (PAN) with ethylene carbonate and dimethyl formamide as plasticizing solvents are prepared by the solution cast technique. These electrolyte films are free standing, transparent and dimensionally stable. Na+ ions are derived from NaI. The structural properties of pure and complex formations have been examined by X-ray diffraction, Fourier transform infrared spectroscopic studies and differential scanning calorimetric studies. The variation of the conductivity with salt concentration ranging from 10 to 40 wt% is studied. The sample containing 30 wt% of NaI exhibits the highest conductivity of 2.35 × 10-4 S cm-1 at room temperature (303 K) and 1 × 10-3 S cm-1 at 373 K. The conductivity-temperature dependence of polymer electrolyte films obeys Arrhenius behavior with activation energy in the range of 0.25-0.46 eV. The transport numbers both electronic ( t e) and ionic ( t i) are evaluated using Wagner's polarization technique. It is revealed that the conducting species are predominantly due to ions. The ionic transport number of highest conducting film is found to be 0.991. Solid-state battery with configuration Na/(PAN + NaI)/(I2 + C + electrolyte) is developed using the highest conducting gel polymer electrolyte system and the discharge characteristics of the cell are evaluated over the load of 100 KΩ.

  15. Reshaping Lithium Plating/Stripping Behavior via Bifunctional Polymer Electrolyte for Room-Temperature Solid Li Metal Batteries.

    PubMed

    Zeng, Xian-Xiang; Yin, Ya-Xia; Li, Nian-Wu; Du, Wen-Cheng; Guo, Yu-Guo; Wan, Li-Jun

    2016-12-14

    High-energy rechargeable Li metal batteries are hindered by dendrite growth due to the use of a liquid electrolyte. Solid polymer electrolytes, as promising candidates to solve the above issue, are expected to own high Li ion conductivity without sacrificing mechanical strength, which is still a big challenge to realize. In this study, a bifunctional solid polymer electrolyte exactly having these two merits is proposed with an interpenetrating network of poly(ether-acrylate) (ipn-PEA) and realized via photopolymerization of ion-conductive poly(ethylene oxide) and branched acrylate. The ipn-PEA electrolyte with facile processing capability integrates high mechanical strength (ca. 12 GPa) with high room-temperature ionic conductance (0.22 mS cm(-1)), and significantly promotes uniform Li plating/stripping. Li metal full cells assembled with ipn-PEA electrolyte and cathodes within 4.5 V vs Li(+)/Li operate effectively at a rate of 5 C and cycle stably at a rate of 1 C at room temperature. Because of its fabrication simplicity and compelling characteristics, the bifunctional ipn-PEA electrolyte reshapes the feasibility of room-temperature solid-state Li metal batteries.

  16. The ion transport mechanism of lithium polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Dai, Hongli

    Lithium polymer electrolytes are of great interest for use in polymer-electrolyte rechargeable batteries. However, the lithium transport mechanism in the polymer electrolyte has not been fully understood, due partly to the lack of a means to characterize a key lithium transport property, the transference number, correctly and efficiently. This research pioneered the use of the electrophoretic nuclear magnetic resonance technique to measure the lithium transference number (TsbLi) of polymer electrolytes. The development of this technique is described. It is shown that the technique is strictly valid regardless of the degree of dissociation of the electrolyte and the measurement protocol is relatively straightforward. As a result, the accuracy of the technique is high compared to existing techniques. The lithium transport mechanism in polymer gel electrolytes are investigated systematically with complementary techniques including vibrational spectroscopy (Raman scattering), nuclear magnetic resonance, and a.c. impedance spectroscopy. The characteristic lithium transport behavior as a function of the temperature, the salt concentration, the anion type, and the polymer matrices is established. Perfluoroimide and perfluoromethide lithium salts always lead to a larger lithium transference number compared to conventional lithium salts. In poly(vinylidene fluororide-hexfloropropylene) based gel electrolytes, the perfluoroimide anion, (CFsb3SOsb3)sb2Nsp-, results in a nearly invariant TsbLi over a wide salt concentration range. In contrast, the CFsb3SOsb3sp- anion results in TsbLi decreasing monotonically with increasing salt concentration. In poly(acrylonitrile), which binds with Lisp+, the TsbLi versus LiCFsb3SOsb3 concentration curve is nearly parabolic. A qualitative model is proposed which defines the important molecular interactions underlying the lithium transport behavior and extends the Fuoss and Onsager theory to systems with extensive ion complexation.

  17. Photophysics of Solid State Structures as Related To: a. Conformation and Morphology of Polyimide. B. Conductivity and Reactivity of Solid Oxide Electrolytes

    NASA Astrophysics Data System (ADS)

    Wachsman, Eric David

    1990-01-01

    The scope of this investigation is broad, from polymeric to ceramic materials, and for the latter includes both solid state kinetics and heterogeneous electrocatalysis. Macroscopic or bulk properties of these materials are investigated by application of physical chemistry on an atomic--molecular scale. Optical (uv-visible and fluorescence) and AC impedance spectroscopy are applied to the investigation of ordering and defect chemistry in these materials. In the study of polyimides we find that upon annealing at elevated temperature the fluorescence emission intensity increases with both temperature and time. This increase in emission intensity is ascribed to the formation of an ordered morphology and an increase in population of a coplanar conformation. These changes in morphology and conformation result in the formation of an intermolecular and an intramolecular charge transfer complex, respectively, which we propose are the fluorescing species in polyimides. Solid oxide electrolytes (SOE) conduct oxygen ions by a vacancy mechanism at elevated temperature. The fluorite structure of Bi_2O _3 has the highest ionic conductivity due to its high concentration of vacant oxygen sites and the resulting high degree of structural disorder. The conductivity of Bi_2O_3 phase stabilized with 20 mol% Er_2O _3 (ESB), was investigated using AC impedance spectroscopy. The conductivity of this material exhibits two activation energies due to an order-disorder transition of the oxygen sublattice at about 600 ^circC. Ordering of the oxygen sublattice upon annealing below the transition temperature results in a decrease in conductivity with time. This reversible conductivity aging phenomenon was found to follow first order kinetics at short times and diffusion limited growth at long times. An endotherm was observed, using differential thermal analysis, whose magnitude increased with the degree of ordering and the ordered structure was found to involve alignment of oxygen vacancies

  18. Solvent-shift strategy to identify suitable polymers to inhibit humidity-induced solid-state crystallization of lacidipine amorphous solid dispersions.

    PubMed

    Sun, Mengchi; Wu, Chunnuan; Fu, Qiang; Di, Donghua; Kuang, Xiao; Wang, Chao; He, Zhonggui; Wang, Jian; Sun, Jin

    2016-04-30

    The solvent-shift strategy was used to identify appropriate polymers that inhibit humidity-induced solid-state crystallization of amorphous solid dispersions (ASDs). Lacidipine with the polymers, PVP-K30, HPMC-E5 or Soluplus, were combined to form amorphous solid dispersions prepared by solvent evaporation. The formulations were characterized by differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier-transform infrared spectroscopy (FT-IR) and were subjected to in vitro dissolution testing. The moisture had a significant impact on the amount dissolved for the solid dispersions. Molecular docking studies established that hydrogen bonding was critical for the stabilization of the solid dispersions. The rank order of the binding energy of the drug-polymer association was Soluplus (-6.21 kcal/mol)>HPMC-E5 (-3.21 kcal/mol)>PVP-K30 (-2.31 kcal/mol). PVP-K30 had the highest water uptake among the polymers, as did ASD system of lacidipine-PVP-K30 ASDs. In the Soluplus ASDs, with its strong drug-polymer interactions and low water uptake, moisture-induced solid-state crystallization was not observed.

  19. Electrochemical and structural evaluation for bulk-type all-solid-state batteries using Li4GeS4-Li3PS4 electrolyte coating on LiCoO2 particles

    NASA Astrophysics Data System (ADS)

    Ito, Yusuke; Otoyama, Misae; Hayashi, Akitoshi; Ohtomo, Takamasa; Tatsumisago, Masahiro

    2017-08-01

    Bulk-type all-solid-state batteries, which use composite electrodes with a powder mixture of active materials and solid electrolytes, are anticipated for large-scale power sources. However, conventional powder mixing protocols are insufficient to maintain ion-conductive pathways within composite electrodes. Herein, sulfide electrolyte coatings have attracted attention as a promising means to overcome this difficulty. We assessed the effects of sulfide electrolyte coatings for active materials on the electrochemical properties and structural changes in all-solid-state cells. A favorable electrode-electrolyte interface was formed by coating significantly small amounts (ca. 3 wt%) of Li4GeS4-Li3PS4 solid electrolyte (SE) onto LiCoO2 particles via vapor phase process. The all-solid-state cell (In/Li2S-P2S5/SE-coated LiCoO2) was charged and discharged with a larger capacity than that using non-SE-coated LiCoO2 particles, indicating that the SE-coating is effective in forming a favorable ion-conductive pathway to LiCoO2 particles. Improvement of the cell performance after heat treatment was considered to derive not only from the enhancement of ionic conductivity in the SE-coating layer, but also from the reduction of voids in the composite electrode. Less ionic resistance and denser environment are beneficial for the Li-ion supply to the deepest part in the composite electrode, which results in more homogeneous electrochemical reaction in all-solid-state cells.

  20. From the bottom up--flexible solid state electrochromic devices.

    PubMed

    Jensen, Jacob; Krebs, Frederik C

    2014-11-12

    Solid-state flexible polymer-based electrochromic devices are fabricated continuously by stacking layers in one direction. This novel bottom-up approach with no need for a lamination step is realized through in situ photo-crosslinking of the electrolyte using a "curing-chamber" fitted to a roll-coater, which lowers the oxygen concentration at the electrolyte surface. This enables fully printed and 2D patterned organic electrochromics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The Use of Solid States Ionic Materials and Devices in Medical Applications

    NASA Astrophysics Data System (ADS)

    Linford, R. G.

    2006-06-01

    Electrolyte materials used in solid state polymer batteries can also be utilised in a special type of drug delivery system called an iontophoretic device. This review will describe the history, applications and limitations of iontophoretic and related systems and also the use of batteries and biofuel cells in medicine.

  2. Solid state cell with anolyte

    SciTech Connect

    Barnette, L. H.; Liang, C. C.

    1985-06-25

    A solid state cell having a solid cathode, a solid electrolyte, and a solid anolyte comprised of at least 50% by volume of ionically conductive materials such as the electrolye and 50% or less by volume of an active metal. The anolyte is either the cell anode or alternatively the anolyte is an additional structural member within said cell positioned between an anode, comprised of the same active metal, and the solid electrolyte.

  3. Highly conductive solid polymer electrolyte membranes based on polyethylene glycol-bis-carbamate dimethacrylate networks

    NASA Astrophysics Data System (ADS)

    Fu, Guopeng; Dempsey, Janel; Izaki, Kosuke; Adachi, Kaoru; Tsukahara, Yasuhisa; Kyu, Thein

    2017-08-01

    In an effort to fabricate highly conductive, stable solid-state polymer electrolyte membranes (PEM), polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction between polyethylene glycol diamine and ethylene carbonate. Subsequently, dimethacrylate groups were chemically attached to both ends of PEGBC to afford polyethylene glycol-bis-carbamate dimethacrylate (PEGBCDMA) precursor having crosslinking capability. The melt-mixed ternary mixtures consisting of PEGBCDMA, succinonitrile plasticizer, and lithium trifluorosulphonyl imide salt were completely miscible in a wide compositional range. Upon photo-crosslinking, the neat PEGBCDMA network was completely amorphous exhibiting higher tensile strength, modulus, and extensibility relative to polyethylene glycol diacrylate (PEGDA) counterpart. Likewise, the succinonitrile-plasticized PEM network containing PEGBCDMA remained completely amorphous and transparent upon photo-crosslinking, showing superionic conductivity, improved thermal stability, and superior tensile properties with improved capacity retention during charge/discharge cycling as compared to the PEGDA-based PEM.

  4. Hybrid materials and polymer electrolytes for electrochromic device applications.

    PubMed

    Thakur, Vijay Kumar; Ding, Guoqiang; Ma, Jan; Lee, Pooi See; Lu, Xuehong

    2012-08-08

    Electrochromic (EC) materials and polymer electrolytes are the most imperative and active components in an electrochromic device (ECD). EC materials are able to reversibly change their light absorption properties in a certain wavelength range via redox reactions stimulated by low direct current (dc) potentials of the order of a fraction of volts to a few volts. The redox switching may result in a change in color of the EC materials owing to the generation of new or changes in absorption band in visible region, infrared or even microwave region. In ECDs the electrochromic layers need to be incorporated with supportive components such as electrical contacts and ion conducting electrolytes. The electrolytes play an indispensable role as the prime ionic conduction medium between the electrodes of the EC materials. The expected applications of the electrochromism in numerous fields such as reflective-type display and smart windows/mirrors make these materials of prime importance. In this article we have reviewed several examples from our research work as well as from other researchers' work, describing the recent advancements on the materials that exhibit visible electrochromism and polymer electrolytes for electrochromic devices. The first part of the review is centered on nanostructured inorganic and conjugated polymer-based organic-inorganic hybrid EC materials. The emphasis has been to correlate the structures, morphologies and interfacial interactions of the EC materials to their electronic and ionic properties that influence the EC properties with unique advantages. The second part illustrates the perspectives of polymer electrolytes in electrochromic applications with emphasis on poly (ethylene oxide) (PEO), poly (methyl methacrylate) (PMMA) and polyvinylidene difluoride (PVDF) based polymer electrolytes. The requirements and approaches to optimize the formulation of electrolytes for feasible electrochromic devices have been delineated. Copyright © 2012 WILEY

  5. Solid-state radioluminescent compositions

    DOEpatents

    Clough, Roger L.; Gill, John T.; Hawkins, Daniel B.; Renschler, Clifford L.; Shepodd, Timothy J.; Smith, Henry M.

    1991-01-01

    A solid state radioluminescent composition for light source comprises an optically clear polymer organic matrix containing tritiated organic materials and dyes capable of "red" shifting primary scintillation emissions from the polymer matrix. The tritiated organic materials are made by reducing, with tritium, an unsaturated organic compound that prior to reduction contains olefinic or alkynylic bonds.

  6. Electrode-Electrolyte Interfaces in Solid Polymer Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Hu, Qichao

    This thesis studies the performance of solid polymer lithium batteries from room temperature to elevated temperatures using mainly electrochemical techniques, with emphasis on the bulk properties of the polymer electrolyte and the electrode-electrolyte interfaces. Its contributions include: 1) Demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence, and improved the conductivity of the graft copolymer electrolyte (GCE) by almost an order of magnitude by changing the ion-conducting block from poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). 2) Identified the rate-limiting step in the battery occurs at the cathode-electrolyte interface using both full cell and symmetric cell electrochemical impedance spectroscopy (EIS), improved the battery rate capability by using the GCE as both the electrolyte and the cathode binder to reduce the resistance at the cathode-electrolyte interface, and used TEM and SEM to visualize the polymer-particle interface (full cells with LiFePO4 as the cathode active material and lithium metal as the anode were assembled and tested). 3) Applied the solid polymer battery to oil and gas drilling application, performed high temperature (up to 210 °C) cycling (both isothermal and thermal cycling), and demonstrated for the first time, current exchange between a solid polymer electrolyte and a liquid lithium metal. Both the cell open-circuit-voltage (OCV) and the overall GCE mass remained stable up to 200 °C, suggesting that the GCE is electrochemically and gravimetrically stable at high temperatures. Used full cell EIS to study the behavior of the various battery parameters as a function of cycling and temperature. 4) Identified the thermal instability of the cell was due to the reactivity of lithium metal and its passivation film at high temperatures, and used Li/GCE/Li symmetric cell

  7. Highly mobile segments in crystalline poly(ethylene oxide)8:NaPF6 electrolytes studied by solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Luo, Huan; Liang, Xinmiao; Wang, Liying; Zheng, Anmin; Liu, Chaoyang; Feng, Jiwen

    2014-02-01

    Two types of high-crystallinity poly(ethylene oxide)/NaPF6 electrolytes with ethylene oxide (EO)/Na molar ratios of 8:1 and 6:1, termed as PEO8:NaPF6 and PEO6:NaPF6 with Mw = 6000 g mol-1 were prepared, and their ionic conductivity, structure, and segmental motions were investigated and compared. PEO8:NaPF6 polymer electrolyte exhibits the room-temperature ionic conductivity 7.7 × 10-7 S cm-1 which is about five times higher than the PEO6:NaPF6. By variable-temperature measurements of static powder spectra and 1H spin-lattice relaxation time in rotation frame (1H T1ρ), we demonstrate that crystalline segments are more highly mobile in the crystalline PEO8:NaPF6 with higher ionic conductivity than in the PEO6:NaPF6 with lower ionic conductivity. The large-angle reorientation motion of polymer segments in the PEO8:NaPF6 onsets at lower temperature (˜233 K) with a low activation energy 0.31 eV that is comparable with that of the pure PEO crystal. Whereas, the large-angle reorientation motion of polymer segments in the PEO6:NaPF6 starts around 313 K with a high activation energy of 0.91 eV. As a result of the temperature-enhanced large-angle reorientations, the 13C static powder lineshape changes markedly from a low-temperature wide pattern with apparent principal values of chemical shift δ33 < δ22 < δ11 to a high-temperature narrow pattern of uniaxial chemical shift anisotropy δ33 > δ22 (δ11). It is suggested that the segmental motion in crystalline PEO-salt complex promotes ionic conductivity.

  8. Dye-impregnated polymer-filled porous glass: a new composite material for solid state dye lasers and laser beam control optical elements (Abstract Only)

    NASA Astrophysics Data System (ADS)

    Koldunov, M. F.; Manenkov, Alexander A.; Sitnikov, N. M.; Dolotov, S. M.

    1994-07-01

    Polymer-filled microporous glass (PFMG) composite materials have been recently proposed as a proper host for dyes to create solid-state dye lasers and laser beam control elements (Q-switchers, etc.) [1,2]. In this paper we report investigation of some laser-related properties of Polymethilmethacrylate (PMAA) - filled porous glass doped with Rhodamine 6G perchiorate (active lasing dye) and 1055 dye (passive bleachable dye): laser induced damage threshold, lasmg efficiency, bleaching efficiency, and microhardness have been measured. All these characteristics have been found to be rather high indicating that PFMG composite materials are perspective hosts for dye impregnation and fabrication highly effective solid-state dye lasers and other laser related elements (Q-switchers, mode-lockers, modeselectors, spatial filters).

  9. Electrical characterization of proton conducting polymer electrolyte based on bio polymer with acid dopant

    SciTech Connect

    Kalaiselvimary, J.; Pradeepa, P.; Sowmya, G.; Edwinraj, S.; Prabhu, M. Ramesh

    2016-05-06

    This study describes the biodegradable acid doped films composed of chitosan and Perchloric acid with different ratios (2.5 wt %, 5 wt %, 7.5 wt %, 10 wt %) was prepared by the solution casting technique. The temperature dependence of the proton conductivity of complex electrolytes obeys the Arrhenius relationship. Proton conductivity of the prepared polymer electrolyte of the bio polymer with acid doped was measured to be approximately 5.90 × 10{sup −4} Scm{sup −1}. The dielectric data were analyzed using Complex impedance Z*, Dielectric loss ε’, Tangent loss for prepared polymer electrolyte membrane with the highest conductivity samples at various temperature.

  10. Electrical characterization of proton conducting polymer electrolyte based on bio polymer with acid dopant

    NASA Astrophysics Data System (ADS)

    Kalaiselvimary, J.; Pradeepa, P.; Sowmya, G.; Edwinraj, S.; Prabhu, M. Ramesh

    2016-05-01

    This study describes the biodegradable acid doped films composed of chitosan and Perchloric acid with different ratios (2.5 wt %, 5 wt %, 7.5 wt %, 10 wt %) was prepared by the solution casting technique. The temperature dependence of the proton conductivity of complex electrolytes obeys the Arrhenius relationship. Proton conductivity of the prepared polymer electrolyte of the bio polymer with acid doped was measured to be approximately 5.90 × 10-4 Scm-1. The dielectric data were analyzed using Complex impedance Z*, Dielectric loss ɛ', Tangent loss for prepared polymer electrolyte membrane with the highest conductivity samples at various temperature.

  11. High temperature lithium cells with solid polymer electrolytes

    DOEpatents

    Yang, Jin; Eitouni, Hany Basam; Singh, Mohit

    2017-03-07

    Electrochemical cells that use electrolytes made from new polymer compositions based on poly(2,6-dimethyl-1,4-phenylene oxide) and other high-softening-temperature polymers are disclosed. These materials have a microphase domain structure that has an ionically-conductive phase and a phase with good mechanical strength and a high softening temperature. In one arrangement, the structural block has a softening temperature of about 210.degree. C. These materials can be made with either homopolymers or with block copolymers. Such electrochemical cells can operate safely at higher temperatures than have been possible before, especially in lithium cells. The ionic conductivity of the electrolytes increases with increasing temperature.

  12. Solid Polymer Electrolyte (SPE) fuel cell technology program

    NASA Technical Reports Server (NTRS)

    1979-01-01

    The overall objectives of the Phase IV Solid Polymer Electrolyte Fuel Cell Technology Program were to: (1) establish fuel cell life and performance at temperatures, pressures and current densities significantly higher than those previously demonstrated; (2) provide the ground work for a space energy storage system based on the solid polymer electrolyte technology (i.e., regenerative H2/O2 fuel cell); (3) design, fabricate and test evaluate a full-scale single cell unit. During this phase, significant progress was made toward the accomplishment of these objectives.

  13. Electrospun nanocomposite fibrous polymer electrolyte for secondary lithium battery applications

    SciTech Connect

    Padmaraj, O.; Rao, B. Nageswara; Jena, Paramananda; Satyanarayana, N.; Venkateswarlu, M.

    2014-04-24

    Hybrid nanocomposite [poly(vinylidene fluoride -co- hexafluoropropylene) (PVdF-co-HFP)/magnesium aluminate (MgAl{sub 2}O{sub 4})] fibrous polymer membranes were prepared by electrospinning method. The prepared pure and nanocomposite fibrous polymer electrolyte membranes were soaked into the liquid electrolyte 1M LiPF{sub 6} in EC: DEC (1:1,v/v). XRD and SEM are used to study the structural and morphological studies of nanocomposite electrospun fibrous polymer membranes. The nanocomposite fibrous polymer electrolyte membrane with 5 wt.% of MgAl{sub 2}O{sub 4} exhibits high ionic conductivity of 2.80 × 10{sup −3} S/cm at room temperature. The charge-discharge capacity of Li/LiCoO{sub 2} coin cells composed of the newly prepared nanocomposite [(16 wt.%) PVdF-co-HFP+(5 wt.%) MgAl{sub 2}O{sub 4}] fibrous polymer electrolyte membrane was also studied and compared with commercial Celgard separator.

  14. Novel Elastomeric Membranes Developed for Polymer Electrolytes in Lithium Batteries

    NASA Technical Reports Server (NTRS)

    Tigelaar, Dean M.; Meador, Maryann B.; Kinder, James D.; Bennett, William R.

    2005-01-01

    Lithium-based polymer batteries for aerospace applications need to be highly conductive from -70 to 70 C. State-of-the-art polymer electrolytes are based on polyethylene oxide (PEO) because of the ability of its ether linkages to solvate lithium ions. Unfortunately, PEO has a tendency to form crystalline regions below 60 C, dramatically lowering conductivity below this temperature. PEO has acceptable ionic conductivities (10(exp -4) to 10(exp -3) S/cm) above 60 C, but it is not mechanically strong. The room-temperature conductivity of PEO can be increased by adding solvent or plasticizers, but this comes at the expense of thermal and mechanical stability. One of NASA Glenn Research Center s objectives in the Polymer Rechargeable System program (PERS) is to develop novel polymer electrolytes that are highly conductive at and below room temperature without added solvents or plasticizers.

  15. Solid polymer battery electrolyte and reactive metal-water battery

    DOEpatents

    Harrup, Mason K.; Peterson, Eric S.; Stewart, Frederick F.

    2000-01-01

    In one implementation, a reactive metal-water battery includes an anode comprising a metal in atomic or alloy form selected from the group consisting of periodic table Group 1A metals, periodic table Group 2A metals and mixtures thereof. The battery includes a cathode comprising water. Such also includes a solid polymer electrolyte comprising a polyphosphazene comprising ligands bonded with a phosphazene polymer backbone. The ligands comprise an aromatic ring containing hydrophobic portion and a metal ion carrier portion. The metal ion carrier portion is bonded at one location with the polymer backbone and at another location with the aromatic ring containing hydrophobic portion. The invention also contemplates such solid polymer electrolytes use in reactive metal/water batteries, and in any other battery.

  16. Ion beam irradiation as a tool to improve the ionic conductivity in solid polymer electrolyte systems

    SciTech Connect

    Manjunatha, H. Kumaraswamy, G. N.; Damle, R.

    2016-05-06

    Solid polymer electrolytes (SPEs) have potential applications in solid state electronic and energy devices. The optimum conductivity of SPEs required for such applications is about 10{sup −1} – 10{sup −3} Scm{sup −1}, which is hard to achieve in these systems. It is observed that ionic conductivity of SPEs continuously increase with increasing concentration of inorganic salt in the host polymer. However, there is a critical concentration of the salt beyond which the conductivity of SPEs decreases due to the formation of ion pairs. In the present study, solid polymer thin films based on poly (ethylene oxide) (PEO) complexed with NaBr salt with different concentrations have been prepared and the concentration at which ion pair formation occurs in PEO{sub x}NaBr is identified. The microstructure of the SPE with highest ionic conductivity is modified by irradiating it with low energy O{sup +1} ion (100 keV) of different fluencies. It is observed that the ionic conductivity of irradiated SPEs increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains due to radiation induced micro structural modification.

  17. Ion beam irradiation as a tool to improve the ionic conductivity in solid polymer electrolyte systems

    NASA Astrophysics Data System (ADS)

    Manjunatha, H.; Damle, R.; Kumaraswamy, G. N.

    2016-05-01

    Solid polymer electrolytes (SPEs) have potential applications in solid state electronic and energy devices. The optimum conductivity of SPEs required for such applications is about 10-1 - 10-3 Scm-1, which is hard to achieve in these systems. It is observed that ionic conductivity of SPEs continuously increase with increasing concentration of inorganic salt in the host polymer. However, there is a critical concentration of the salt beyond which the conductivity of SPEs decreases due to the formation of ion pairs. In the present study, solid polymer thin films based on poly (ethylene oxide) (PEO) complexed with NaBr salt with different concentrations have been prepared and the concentration at which ion pair formation occurs in PEOxNaBr is identified. The microstructure of the SPE with highest ionic conductivity is modified by irradiating it with low energy O+1 ion (100 keV) of different fluencies. It is observed that the ionic conductivity of irradiated SPEs increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains due to radiation induced micro structural modification.

  18. Ion-Conductive Properties of a Polymer Electrolyte Based on Ethylene Carbonate/Ethylene Oxide Random Copolymer.

    PubMed

    Morioka, Takashi; Nakano, Koji; Tominaga, Yoichi

    2017-02-21

    A random copolymer of ethylene oxide with CO2 , namely, poly(ethylene carbonate/ethylene oxide) (P(EC/EO)), has been synthesized as a novel candidate for polymer electrolytes. Electrolyte composed of P(EC/EO) and lithium bis(fluorosulfonyl)imide has an ionic conductivity of 0.48 mS cm(-1) and a Li transference number (t + ) of 0.66 at 60 °C. To study ion-conductive behavior of P(EC/EO)-based electrolytes, the Fourier transform infrared (FT-IR) technique is used to analyze the interactions between Li(+) and functional groups of the copolymer. The carbonate groups may interact preferentially with Li(+) rather than the ether groups in P(EC/EO). This study suggests that copolymerization of carbonate and flexible ether units can realize both high conductivity and t + for polymer electrolytes. High-performance P(EC/EO) electrolyte is expected to be a candidate material for use in all-solid-state batteries.

  19. Proton conducting, high modulus polymer electrolyte membranes by polymerization-induced microphase separation

    NASA Astrophysics Data System (ADS)

    Chopade, Sujay; Hillmyer, Marc; Lodge, Timothy

    Robust solid-state polymer electrolyte membranes (PEMs) are vital for designing next-generation lithium-ion batteries and high-temperature fuel cells. However, the performance of diblock polymer electrolytes is generally limited by poor mechanical stability and network defects in the conducting pathways. We present the in-situ preparation of robust cross-linked PEMs via polymerization-induced microphase separation, and incorporation of protic ionic liquid (IL) into one of the microphase separated domains. The facile design strategy involves a delicate balance between the controlled growth of polystyrene from a poly(ethylene oxide) macro-chain transfer agent (PEO-CTA) and simultaneous chemical cross-linking by divinylbenzene in the presence of IL. Small angle X-ray scattering and transmission electron microscopy confirmed the formation of a disordered structure with bicontinuous morphology and a characteristic domain size of order 20 nm. The long-range continuity of the PEO/protic IL conducting nanochannels and cross-linked polystyrene domains imparts high thermal and mechanical stability to the PEMs, with elastic modulus approaching 10 MPa and a high ionic conductivity of 15 mS/cm at 180 °C.

  20. Performance of electric double layer capacitors with polymer gel electrolytes

    SciTech Connect

    Ishikawa, Masashi; Kishino, Takahiro; Katada, Naoji; Morita, Masayuki

    2000-07-01

    Polymer gel electrolytes consisting of poly(vinylidene fluoride) (PVdF), tetraethylammonium tetrafluoroborate (TEABF{sub 4}), and propylene carbonate (PC) as a plasticizer have been investigated for electric double layer capacitors. The PVdF gel electrolytes showed high ionic conductivity (ca. 6 mS/cm at 298 K). To assemble model capacitors with the PVdF gel electrolytes and activated carbon fiber cloth electrodes, a pair of the fixed electrodes was soaked in a precursor solution containing PC, PVdF, and TEABF{sub 4}, followed by evaporation of the PC solvent in a vacuum oven. The resulting gel electrolytes were in good contact with the electrodes. The model capacitors with the PVdF gel electrolytes showed a large value of capacitance and high coulombic efficiency in operation voltage ranges of 1--2 and 1--3 V. It is worth noting that the capacitors with the PVdF electrolytes showed long voltage retention in a self-discharge test. These good characteristics of the gel capacitors were comparable to those of typical double layer capacitors with a liquid organic electrolyte containing PC and TEABF{sub 4}; rather, the voltage retentivity of the PVdF gel capacitors was much superior to that of the capacitors with the organic electrolyte.

  1. Fabrication of ultrathin solid electrolyte membranes of β-Li3PS4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

    SciTech Connect

    Wang, Hui; Hood, Zachary D.; Xia, Younan; Liang, Chengdu

    2016-04-25

    All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li3PS4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreased to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li3PS4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.

  2. Fabrication of ultrathin solid electrolyte membranes of β-Li3PS4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

    SciTech Connect

    Wang, Hui; Hood, Zachary D.; Xia, Younan; Liang, Chengdu

    2016-04-25

    All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li3PS4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreased to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li3PS4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.

  3. PEO-based polymer electrolytes for secondary lithium batteries

    NASA Astrophysics Data System (ADS)

    Stowe, Micah Kristin

    Polyethers mixed with lithium salts are excellent candidates for electrolytes in rechargeable lithium batteries. Polyether systems with low crystallinity result in fast ion mobility and therefore high conductivities. In this work the properties of several poly(ethylene oxide) based electrolytes are examined with an emphasis on systems with reduced crystallinity including, composite polymer electrolytes, oligomeric polyethers, and (AB) microblock copolymers. Highly conductive and processable composite polymer electrolytes were made using surface functionalized fumed silica fillers and PEGDME-500 (LiClO 4, O/Li = 20). The fillers were both hydrophobic and cross-linkable and formed an open three-dimensional network in the electrolytes due to van der Waals forces. The open network allowed for high ionic mobility and provided for the mechanical stability of the composite. Methacrylate monomers of differing hydrophobicity were added to cross-link the silica network and impart permanent mechanical stability. The optical, conductive, thermal, mechanical, and kinetic properties of the composites are examined as a function of monomer hydrophobicity and filler surface chemistry. It was found that hydrophobic monomers such as butyl methacrylate and octyl methacrylate preferentially phase separate onto the filler surface while hydrophilic methyl methacrylate is soluble in the electrolyte phase. The composites were both photochemically and thermally cured to 85--95% conversion of monomer to polymer. Hydrophilic monomers such as methyl methacrylate are more compatible with the electrolyte after polymerization and therefore provide for better mechanical properties in the composite. However, unpolymerized methyl methacrylate can react at the electrodes resulting in increased interfacial resistance. A branched oligomeric polyether, star(12)PEO, was prepared and characterized. Electrolytes formed from star(12)PEO and LiClO4 were characterized by DSC and variable temperature impedance

  4. Solid State Research

    DTIC Science & Technology

    1990-11-15

    Alo .3Gao.7As confining layers. 38 IX Figure No. Page 3-2 Schematic structure and energy diagram of AlInGaAs/AlGaAs SCH SQW diode laser. 39 3-3...Lithography Photooxidation of a-Conjugated Si-Si Network Polymers High-Power Solid-State Laser Radar Technology Heat Driven Cryocoolers for...M.J. Nichols, K.B. Parker, CD. Rabe, S. Rathman, D.D. Smith, F.W., III Vera , A. xxvn ELECTROOPTICAL DEVICES ANALOG DEVICE TECHNOLOGY R.C

  5. Study on (100-x)(70Li2S-30P2S5)-xLi2ZrO3 glass-ceramic electrolyte for all-solid-state lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lu, Penghao; Ding, Fei; Xu, Zhibin; Liu, Jiaquan; Liu, Xingjiang; Xu, Qiang

    2017-07-01

    A novel glass-ceramic electrolyte of (100-x)(70Li2S-30P2S5)-xLi2ZrO3 (x = 0, 1, 2, 5) is successfully prepared by a vibratory ball-milling method and followed by a heat-treatment process. Composition of the ternary sulfide electrolyte and the heat-treatment process are optimized by physical characterizations and electrochemical measurements. The testing results show that the optimal substitution quantity of Li2ZrO3 into the Li2S-P2S5 electrolyte substrate is 1 mol %. An appropriate heat-treatment temperature of 99(70Li2S-30P2S5)-1Li2ZrO3 glass-ceramic electrolyte is 285 °C. Among the as-prepared ternary electrolyte samples, 99(70Li2S-30P2S5)-1Li2ZrO3 glass-ceramic electrolyte may exhibit the highest conductivity of 2.85 × 10-3 S cm-1 at room temperature, which is much higher than that of the 70Li2S-30P2S5 glass-ceramic electrolyte. Compared to that of the all-solid-state lithium-ion battery of LiCoO2/70Li2S-30P2S5/In-Li, discharge capacities of all-solid-state lithium-ion battery of LiCoO2/99(70Li2S-30P2S5)-1Li2ZrO3/In-Li may increase 41.0% at the 10th charge-discharge cycle and 21.9% at the 50th charge-discharge cycle, respectively. Furthermore, electrochemical impedance spectroscopy (EIS) analyses of all-solid-state lithium-ion batteries reveal that addition of Li2ZrO3 into the Li2S-P2S5 electrolyte substrate may decrease the interfacial resistance between the electrodes and solid electrolyte. The improvement of electrochemical performances of 99(70Li2S-30P2S5)-1Li2ZrO3 glass-ceramic electrolyte is ascribed to both the stable crystal structure and a high lithium-ion diffusion coefficient of Li2ZrO3.

  6. Preparation and characterization of cross-linked composite polymer electrolytes

    SciTech Connect

    Hou, J.; Baker, G.L.

    1998-11-01

    Cross-linkable composite electrolytes were prepared from poly(ethylene glycol) dimethyl ether (PEGDME)-500, LiClO{sub 4}, fumed silica, and 10 wt % methyl, butyl, or octyl methacrylate. The silicas used were chemically modified by attaching methacrylate groups to the silica surface through C{sub 8} and C{sub 3} tethers. Before cross-linking, the electrolytes were thixotropic and had ionic conductivities of >2 {times} 10{sup {minus}4} S/cm. After ultraviolet (UV)-induced cross-linking, the electrolytes were rubbery and dimensionally stable, and the conductivities were unchanged. Conductivity, extraction, and thermal analysis data all support a model where the added methacrylate monomer and growing polymer chains phase separate from the electrolyte phase during photopolymerization to yield a methacrylate-rich silica/polymer phase and little or no polymer in the PEGDME-500 phase. Thus, the mechanical properties of the composite electrolyte and its ionic conductivity are decoupled and can be optimized independently.

  7. Inkjet printed organic electrochemical transistors with highly conducting polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Afonso, Mónica; Morgado, Jorge; Alcácer, Luís

    2016-10-01

    Organic Electrochemical Transistors (OECTs) were fabricated with two kinds of highly conducting polymer electrolytes, one with cations of small dimensions (Li+) and the other with cations of large dimensions (1-ethyl-3-methylimidazolium, EMI+). All OECTs exhibit transconductance values in the millisiemens range. Those with the larger EMI+ cations reach higher transconductance values and the saturated region of their I(V) characteristics extends to drain negative voltages of the order of -2 V without breakdown. These OECTs aim at potential applications for which it is relevant to use a solid polymer electrolyte instead of an aqueous electrolyte, namely, for integration in complex devices or in sensors and transducers where the electrolyte film may act as a membrane to prevent direct contact of the active material (PEDOT:PSS) with the biological media. The choice of electrolytes with cations of disparate sizes aims at assessing the nature (Faradaic or capacitive) of the processes occurring at the electrolyte/channel interface. The results obtained are consistent with a Faradaic-based operation mechanism.

  8. Novel, Solvent-Free, Single Ion-Conductive Polymer Electrolytes

    DTIC Science & Technology

    2008-02-01

    SUBJECT TERMS EOARD, Power, Electrochemistry, Batteries 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT UL 18, NUMBER OF PAGES...the diffraction patterns of the LiBOB-PEO with the LiTf and LiBF4 -based polymer electrolyte. As can be seen from the Figures, the XRD lines

  9. Characterization of plasticized PEO-PAM blend polymer electrolyte system

    NASA Astrophysics Data System (ADS)

    Dave, Gargi; Kanchan, Dinesh

    2017-05-01

    Present study reports characterization studies of NaCF3SO3 based PEO-PAM Blend Polymer Electrolyte (BPE) system with varying amount of EC+PC as plasticizer prepared by solution cast technique. Structural analysis and surface topography have been performed using FTIR and SEM studies. To understand, thermal properties, DSC studies have been undertaken in the present paper

  10. Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

    NASA Technical Reports Server (NTRS)

    Bronstein, Lyudmila M.; Karlinsey, Robert L.; Ritter, Kyle; Joo, Chan Gyu; Stein, Barry; Zwanziger, Josef W.

    2003-01-01

    This paper reports synthesis, structure, and properties of novel hybrid solid polymer electrolytes (SPE's) consisting of organically modified aluminosilica (OM-ALSi), formed within a poly(ethylene oxide)-in-salt (Li triflate) phase. To alter the structure and properties we fused functionalized silanes containing poly(ethylene oxide) (PEO) tails or CN groups.

  11. Solid state and sonochemical syntheses of nano lead(II) chloride and bromide coordination polymers from its nitrate analog via mechanochemical crystal to crystal transformations.

    PubMed

    Hashemi, Lida; Morsali, Ali

    2014-07-01

    Reversible crystal-to-crystal transformations of 3D lead(II) coordination polymers with the ligand 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-bpdh), from nitrate analoge [Pb(4-bpdh)(NO3)2(H2O)]n (1) to [Pb(4-bpdh)(NO3)(Br)]n (2), [Pb(4-bpdh)(Br)2]n (3), [Pb(4-bpdh)(NO3)(Cl)]n (4) and [Pb(4-bpdh)(Cl)2]n (5) by solid state anion-replacement processes under mechanochemical reactions, have been studied. The reversible solid state structural transformations of compounds 1-5, by anion-replacement processes under mechanochemical reaction, have been verified by PXRD measurements. Nanoparticles of compounds were synthesized by sonochemical process and characterized by scanning electron microscopy (SEM), powder X-ray diffraction, IR spectroscopy and elemental analyses. The SEM images showed that morphology change occurs during solid state anion-replacements of nanocrystals.

  12. Raman spectroscopy for the in-line polymer-drug quantification and solid state characterization during a pharmaceutical hot-melt extrusion process.

    PubMed

    Saerens, L; Dierickx, L; Lenain, B; Vervaet, C; Remon, J P; De Beer, T

    2011-01-01

    The aim of this study was to evaluate the suitability of Raman spectroscopy as a Process Analytical Technology (PAT) tool for the in-line determination of the active pharmaceutical ingredient (API) concentration and the polymer-drug solid state during a pharmaceutical hot-melt extrusion process. For in-line API quantification, different metoprolol tartrate (MPT)--Eudragit® RL PO mixtures, containing 10%, 20%, 30% and 40% MPT, respectively, were extruded and monitored in-line in the die using Raman spectroscopy. A PLS model, regressing the MPT concentrations versus the in-line collected Raman spectra, was developed and validated, allowing real-time API concentration determination. The correlation between the predicted and real MPT concentrations of the validation samples is acceptable (R(2)=0.997). The predictive performance of the calibration model is rated by the root mean square error of prediction (RMSEP), which is 0.59%. Two different polymer-drug mixtures were prepared to evaluate the suitability of Raman spectroscopy for in-line polymer-drug solid state characterization. Mixture 1 contained 90% Eudragit® RS PO and 10% MPT and was extruded at 140°C, hence producing a solid solution. Mixture 2 contained 60% Eudragit® RS PO and 40% MPT and was extruded at 105°C, producing a solid dispersion. The Raman spectra collected during these extrusion processes provided two main observations. First, the MPT Raman peaks in the solid solution broadened compared to the corresponding solid dispersion peaks, indicating the presence of amorphous MPT. Second, peak shifts appeared in the spectra of the solid dispersion and solid solution compared to the physical mixtures, suggesting interactions between Eudragit® RS PO and MPT, most likely hydrogen bonds. These shifts were larger in the spectra of the solid solution. DSC analysis confirmed these Raman solid state observations and the interactions seen in the spectra. Raman spectroscopy is a potential PAT-tool for in

  13. Lithium dendrite growth mechanisms in polymer electrolytes and prevention strategies.

    PubMed

    Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat

    2017-08-09

    Future lithium-ion batteries must use lithium metal anodes to fulfill the demands of high energy density applications with the potential to enable affordable electric cars with 350-mile range. However, dendrite growth during charging prevents the commercialization of this technology. It has been demonstrated that the presence of a compressive mechanical stress field around a dendritic protrusion prevents growth. Several techniques based on this concept, such as protective layers, externally applied pressure and solid electrolytes have been investigated by other researchers. Because of the low coulombic efficiencies associated with the stiff protective layers and high-pressure conditions, implementation of these techniques in commercial cells is complicated. Polymer-based solid electrolytes demonstrate better efficiency and capacity retention capabilities. However, dendrite growth is still possible in polymer electrolytes at higher current densities. The simulations described in this article provide guidance on the conditions under which dendrite growth is possible in polymer cells and targets for material properties needed for dendrite prevention. Increasing the elastic modulus of the electrolyte prevents the growth of dendritic protrusions in two ways: (i) higher compressive mechanical stress leads to reduced exchange current density at the protrusion peak compared to the valley, and (ii) plastic deformation of lithium metal results in reduction of the height of the dendritic protrusion. A phase map is constructed, showing the range of operation (applied current) and design (electrolyte elastic modulus) parameters that corresponds to stable lithium deposition. It is found that increasing the yield strength of the polymer electrolyte plays a significant role in preventing dendrite growth in lithium metal anodes, providing a new avenue for further exploration.

  14. Status and applicability of solid polymer electrolyte technology to electrolytic hydrogen and oxygen production

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.

    1973-01-01

    The solid polymer electrolyte (SPE) water electrolysis technology is presented as a potential energy conversion method for wind driven generator systems. Electrolysis life and performance data are presented from laboratory sized single cells (7.2 sq in active area) with high cell current density selected (1000 ASF) for normal operation.

  15. Solid-state lithium battery

    DOEpatents

    Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross

    2014-11-04

    The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

  16. Room temperature solid-state synthesis of a conductive polymer for applications in stable I₂-free dye-sensitized solar cells.

    PubMed

    Kim, Byeonggwan; Koh, Jong Kwan; Kim, Jeonghun; Chi, Won Seok; Kim, Jong Hak; Kim, Eunkyoung

    2012-11-01

    A solid-state polymerizable monomer, 2,5-dibromo-3,4-propylenedioxythiophene (DBProDOT), was synthesized at 25 °C to produce a conducting polymer, poly(3,4-propylenedioxythiophene) (PProDOT). Crystallographic studies revealed a short interplane distance between DBProDOT molecules, which was responsible for polymerization at low temperature with a lower activation energy and higher exothermic reaction than 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) or its derivatives. Upon solid-state polymerization (SSP) of DBProDOT at 25 °C, PProDOT was obtained in a self-doped state with tribromide ions and an electrical conductivity of 0.05 S cm⁻¹, which is considerably higher than that of chemically-polymerized PProDOT (2×10⁻⁶ S cm⁻¹). Solid-state ¹³C NMR spectroscopy and DFT calculations revealed polarons in PProDOT and a strong perturbation of carbon nuclei in thiophenes as a result of paramagnetic broadening. DBProDOT molecules deeply penetrated and polymerized to fill nanocrystalline TiO₂ pores with PProDOT, which functioned as a hole-transporting material (HTM) for I₂-free solid-state dye-sensitized solar cells (ssDSSCs). With the introduction of an organized mesoporous TiO₂ (OM-TiO₂) layer, the energy conversion efficiency reached 3.5 % at 100 mW cm⁻², which was quite stable up to at least 1500 h. The cell performance and stability was attributed to the high stability of PProDOT, with the high conductivity and improved interfacial contact of the electrode/HTM resulting in reduced interfacial resistance and enhanced electron lifetime. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Cation Transport in Polymer Electrolytes: A Microscopic Approach

    NASA Astrophysics Data System (ADS)

    Maitra, A.; Heuer, A.

    2007-06-01

    A microscopic theory for cation diffusion in polymer electrolytes is presented. Based on a thorough analysis of molecular dynamics simulations on poly(ethylene) oxide with LiBF4, the mechanisms of cation dynamics are characterized. Cation jumps between polymer chains can be identified as renewal processes. This allows us to obtain an explicit expression for the lithium ion diffusion constant DLi by invoking polymer-specific properties such as the Rouse dynamics. This extends previous phenomenological and numerical approaches. In particular, the chain length dependence of DLi can be predicted and compared with experimental data. This dependence can be fully understood without referring to entanglement effects.

  18. Cation transport in polymer electrolytes: a microscopic approach.

    PubMed

    Maitra, A; Heuer, A

    2007-06-01

    A microscopic theory for cation diffusion in polymer electrolytes is presented. Based on a thorough analysis of molecular dynamics simulations on poly(ethylene) oxide with LiBF4, the mechanisms of cation dynamics are characterized. Cation jumps between polymer chains can be identified as renewal processes. This allows us to obtain an explicit expression for the lithium ion diffusion constant DLi by invoking polymer-specific properties such as the Rouse dynamics. This extends previous phenomenological and numerical approaches. In particular, the chain length dependence of DLi can be predicted and compared with experimental data. This dependence can be fully understood without referring to entanglement effects.

  19. Li conductivity in siloxane-based polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Stacy, Eric; Fan, Fei; Feng, Hongbo; Gainaru, Catalin; Mays, Jimmy; Sokolov, Alexei

    Polymer electrolytes containing lithium ions are ideal candidates for electrochemical devices and energy storage applications. Understanding their ionic transport mechanism is the key for rational designing of highly conductive polymer matrices. Complementing dielectric spectroscopy investigations by results from rheology and differential scanning calorimetry we focused on the interplay between dynamics of lithium ions and the polymer matrix based on polysiloxane backbone. Our results demonstrate that the conductivity and the degree of decoupling between ion dynamics and structural relaxation depend strongly not only on the ions concentration, but also on the polarity and size of the polymeric side-groups. Chemical Science Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States.

  20. An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes.

    PubMed

    Fattah, N F A; Ng, H M; Mahipal, Y K; Numan, Arshid; Ramesh, S; Ramesh, K

    2016-06-06

    Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge-discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g(-1), which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application.

  1. An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes

    PubMed Central

    Fattah, N. F. A.; Ng, H. M.; Mahipal, Y. K.; Numan, Arshid; Ramesh, S.; Ramesh, K.

    2016-01-01

    Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge–discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g−1, which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application. PMID:28773573

  2. Electrochemical sensor based on conductive polymer electrolyte

    SciTech Connect

    Ribes, C.; Cisneros, B.; Noding, S.A.; Ribes, A.J.

    1995-12-31

    A novel conductive polymer film has been incorporated into an electrochemical sensor for the determination of toxic gases. The conductive film consists of an inert polymer, a completing agent, and a salt. A variety of gases can be determined with this sensor. The specific detection of sulfuryl fluoride (SO{sub 2}F{sub 2}) in air will be discussed as an example of the capability and flexibility of technology.

  3. Highly mobile segments in crystalline poly(ethylene oxide){sub 8}:NaPF{sub 6} electrolytes studied by solid-state NMR spectroscopy

    SciTech Connect

    Luo, Huan; Liang, Xinmiao; Wang, Liying; Zheng, Anmin; Liu, Chaoyang; Feng, Jiwen

    2014-02-21

    Two types of high-crystallinity poly(ethylene oxide)/NaPF{sub 6} electrolytes with ethylene oxide (EO)/Na molar ratios of 8:1 and 6:1, termed as PEO{sub 8}:NaPF{sub 6} and PEO{sub 6}:NaPF{sub 6} with M{sub w} = 6000 g mol{sup −1} were prepared, and their ionic conductivity, structure, and segmental motions were investigated and compared. PEO{sub 8}:NaPF{sub 6} polymer electrolyte exhibits the room-temperature ionic conductivity 7.7 × 10{sup −7} S cm{sup −1} which is about five times higher than the PEO{sub 6}:NaPF{sub 6}. By variable-temperature measurements of static powder spectra and {sup 1}H spin-lattice relaxation time in rotation frame ({sup 1}H T{sub 1ρ}), we demonstrate that crystalline segments are more highly mobile in the crystalline PEO{sub 8}:NaPF{sub 6} with higher ionic conductivity than in the PEO{sub 6}:NaPF{sub 6} with lower ionic conductivity. The large-angle reorientation motion of polymer segments in the PEO{sub 8}:NaPF{sub 6} onsets at lower temperature (∼233 K) with a low activation energy 0.31 eV that is comparable with that of the pure PEO crystal. Whereas, the large-angle reorientation motion of polymer segments in the PEO{sub 6}:NaPF{sub 6} starts around 313 K with a high activation energy of 0.91 eV. As a result of the temperature-enhanced large-angle reorientations, the {sup 13}C static powder lineshape changes markedly from a low-temperature wide pattern with apparent principal values of chemical shift δ{sub 33} < δ{sub 22} < δ{sub 11} to a high-temperature narrow pattern of uniaxial chemical shift anisotropy δ{sub 33} > δ{sub 22} (δ{sub 11}). It is suggested that the segmental motion in crystalline PEO-salt complex promotes ionic conductivity.

  4. International Symposium on Polymer Electrolytes (1st)

    DTIC Science & Technology

    1987-06-01

    PULYPHOSPHAZENE-CROWN ETHERS A series of polyphosphazenes with pendant crown ethers have been prepared . A 16-crown-5 unit was attached to the poly phosphazene...linked to the low cationic transport numbers persisted, as was to be expected. We decided to prepare and test similar networks in which the ionic (or...electrolytes in battery set-up. Finally, suggestions will be put forward concerning the preparation of better ionomeric networks. REFERENCES I - P.V. WRIGHT

  5. Advanced High Energy Lithium Polymer Electrolyte Battery

    DTIC Science & Technology

    2007-11-02

    of the two phase nature of the latter materials.5,6 These materials are also always intrinsically ’ wet ’ in physical appearance. The above...into polymeric matrix of respectively PVC or PAN and radiation polymerized polyethers (so called gel or " wet " electrolytes). In spite of rather...The most widely studied material was polyethylene oxide ) (PEO), incorporating lithium salts such as LiC104 and LiCF3S03. This material however

  6. Polymer-electrolyte-gated nanowire synaptic transistors for neuromorphic applications

    NASA Astrophysics Data System (ADS)

    Zou, Can; Sun, Jia; Gou, Guangyang; Kong, Ling-An; Qian, Chuan; Dai, Guozhang; Yang, Junliang; Guo, Guang-hua

    2017-09-01

    Polymer-electrolytes are formed by dissolving a salt in polymer instead of water, the conducting mechanism involves the segmental motion-assisted diffusion of ion in the polymer matrix. Here, we report on the fabrication of tin oxide (SnO2) nanowire synaptic transistors using polymer-electrolyte gating. A thin layer of poly(ethylene oxide) and lithium perchlorate (PEO/LiClO4) was deposited on top of the devices, which was used to boost device performances. A voltage spike applied on the in-plane gate attracts ions toward the polymer-electrolyte/SnO2 nanowire interface and the ions are gradually returned after the pulse is removed, which can induce a dynamic excitatory postsynaptic current in the nanowire channel. The SnO2 synaptic transistors exhibit the behavior of short-term plasticity like the paired-pulse facilitation and self-adaptation, which is related to the electric double-effect regulation. In addition, the synaptic logic functions and the logical function transformation are also discussed. Such single SnO2 nanowire-based synaptic transistors are of great importance for future neuromorphic devices.

  7. Disentangled solid state and metastable polymer melt; a solvent free route to high-modulus high-strength tapes and films of UHMWPE

    NASA Astrophysics Data System (ADS)

    Rastogi, Sanjay

    2013-03-01

    Ultra High Molecular Weight Polyethylene (UHMWPE) having average molar mass greater than a million g/mol is an engineering polymer. Due to its light-weight, high abrasion resistance and biocompatibility it is used for demanding applications such as body armour, prostheses etc. At present, because of its high melt viscosity to achieve the uniaxial/biaxial properties in the form of fibers/films the polymer is processed via solution route where nearly 95wt% of the solvent is used to process 5wt% of the polymer. In past several attempts have been made to process the polymer without using any solvent. However, compared to the solvent processing route the achieved mechanical properties were rather poor. Here we show that by controlled synthesis it is feasible to obtain UHMWPE that could be processed free of solvent to make uniaxial tapes and biaxial films, having unprecedented mechanical properties, exceeding that of the solution spun fibers. We address some of the fundamental aspects of chemistry, physics, rheology and processing for the development of desired morphological features to achieve the ultimate mechanical properties in tapes and films. The paper will also address the metastable melt state obtained on melting of the disentangled crystals and its implication on rheology in linear and nonlinear viscoelastic region. Solid state NMR studies will be applied to establish disentangled state in solid state to the polymerisation conditions. References: Macromolecules 2011, 44(14), 5558-5568; Nature Materials 2005, 4, 635-641; Phys Rev Lett 2006, 96(21), 218303-218205. The authors acknowledge financial support by the Dutch Polymer Institute.

  8. Low Crossover Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

    NASA Technical Reports Server (NTRS)

    Prakash, G. K. Surya; Smart, Marshall; Atti, Anthony R.; Olah, George A.; Narayanan, S. R.; Valdez, T.; Surampudi, S.

    1996-01-01

    Direct Methanol Fuel Cells (DMFC's) using polymer electrolyte membranes are promising power sources for portable and vehicular applications. State of the art technology using Nafion(R) 117 membranes (Dupont) are limited by high methanol permeability and cost, resulting in reduced fuel cell efficiencies and impractical commercialization. Therefore, much research in the fuel cell field is focused on the preparation and testing of low crossover and cost efficient polymer electrolyte membranes. The University of Southern California in cooperation with the Jet Propulsion Laboratory is focused on development of such materials. Interpenetrating polymer networks are an effective method used to blend polymer systems without forming chemical links. They provide the ability to modify physical and chemical properties of polymers by optimizing blend compositions. We have developed a novel interpenetrating polymer network based on poly (vinyl - difluoride)/cross-linked polystyrenesulfonic acid polymer composites (PVDF PSSA). Sulfonation of polystyrene accounts for protonic conductivity while the non-polar, PVDF backbone provides structural integrity in addition to methanol rejection. Precursor materials were prepared and analyzed to characterize membrane crystallinity, stability and degree of interpenetration. USC JPL PVDF-PSSA membranes were also characterized to determine methanol permeability, protonic conductivity and sulfur distribution. Membranes were fabricated into membrane electrode assemblies (MEA) and tested for single cell performance. Tests include cell performance over a wide range of temperatures (20 C - 90 C) and cathode conditions (ambient Air/O2). Methanol crossover values are measured in situ using an in-line CO2 analyzer.

  9. Solid State Humidity Sensors

    NASA Astrophysics Data System (ADS)

    Chang, Song-Lin

    There are only a few solid state humidity sensors available today. Most of those sensors use a porous oxide material as a principal part of the device. The devices work on the basis of a change in resistance as the moisture in the air varies. In this experiment, two solid state humidity sensors have been developed for use under practical conditions. One is a Polymer Oxide Semiconductor device with a POLYOX film that absorbs the moisture from the air. The amount of water dipoles absorbed by the polymer is a function of relative humidity. This sensor can measure relative humidity from 20% to 90%. The other is a Dew Point sensor. The sensor is in contact with the upper surface of a miniature Peltier cooler. Water molecules deposited on the sensor surface cause the electrical current through the sensor to increase. The operator adjusts the temperature of the Peltier cooler until a saturated current through the sensor is reached. About one min. is required to measure low relative humidities. The Dew Point sensor can measure a range of relative humidities of 30% to 80%.

  10. Efficiency enhancement in dye sensitized solar cells using gel polymer electrolytes based on a tetrahexylammonium iodide and MgI2 binary iodide system.

    PubMed

    Bandara, T M W J; Dissanayake, M A K L; Jayasundara, W J M J S R; Albinsson, I; Mellander, B-E

    2012-06-28

    Quasi-solid-state dye-sensitized solar cells have drawn the attention of scientists and technologists as a potential candidate to supplement future energy needs. The conduction of iodide ions in quasi-solid-state polymer electrolytes and the performance of dye sensitized solar cells containing such electrolytes can be enhanced by incorporating iodides having appropriate cations. Gel-type electrolytes, based on PAN host polymers and mixture of salts tetrahexylammonium iodide (Hex4N(+)I(-)) and MgI2, were prepared by incorporating ethylene carbonate and propylene carbonate as plasticizers. The salt composition in the binary mixture was varied in order to optimize the performance of solar cells. The electrolyte containing 120% Hex4N(+)I(-) with respect to weight of PAN and without MgI2 showed the highest conductivity out of the compositions studied, 2.5 × 10(-3) S cm(-1) at 25 °C, and a glass transition at -102.4 °C. However, the electrolyte containing 100% Hex4N(+)I(-) and 20% MgI2 showed the best solar cell performance highlighting the influence of the cation on the performance of the cell. The predominantly ionic behaviour of the electrolytes was established from the dc polarization data and all the electrolytes exhibit iodide ion transport. Seven different solar cells were fabricated employing different electrolyte compositions. The best cell using the electrolyte with 100% Hex4N(+)I(-) and 20% MgI2 with respect to PAN weight showed 3.5% energy conversion efficiency and 8.6 mA cm(-2) short circuit current density.

  11. Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

    PubMed

    Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

    2017-09-04

    Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li(+) transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Electrochemical properties of composite polymer electrolyte applied to rechargeable lithium polymer battery

    NASA Astrophysics Data System (ADS)

    Matoba, Yasuo; Matsui, Shohei; Tabuchi, Masato; Sakai, Takaaki

    High-molecular-weight comb-shaped polyethers, poly(ethylene oxide-co-2-(2-methoxyethoxy) ethyl glycidyl ether-co-allyl glycidyl ether) (P(EO/EM/AGE)) and poly(ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether) (P(EO/EM)), were synthesized and used for the preparation of the all solid polymer electrolyte and the composite polymer electrolyte combined with a plasticizer Star-EO-OMe, pentaerythritol tetrakis(2-methoxyethyl ether), which shows low vapor pressure, respectively. Some electrochemical properties of the polymer electrolytes and performances of the cell consisting of lithium/polymer electrolyte/LiCoO 2 were studied. The addition of Star-EO-OMe to polymer electrolyte brought about a large increase in ionic conductivity. The composite electrolyte containing 50 wt.% of Star-EO-OMe complexed with LiTFSI, lithium bis(trifluoromethylsulfonyl)imide, exhibited high ionic conductivity in the order of 10 -4 S cm -1 at 10 °C and approximately 10 -5 S cm -1 at -20 °C. The cell performance was also improved by the addition of Star-EO-OMe.

  13. High Capacity, Superior Cyclic Performances in All-Solid-State Lithium-Ion Batteries Based on 78Li2S-22P2S5 Glass-Ceramic Electrolytes Prepared via Simple Heat Treatment.

    PubMed

    Zhang, Yibo; Chen, Rujun; Liu, Ting; Shen, Yang; Lin, Yuanhua; Nan, Ce-Wen

    2017-08-30

    Highly Li-ion conductive 78Li2S-22P2S5 glass-ceramic electrolytes were prepared by simple heat treatment of the glass phase obtained via mechanical ball milling. A high ionic conductivity of ∼1.78 × 10(-3) S cm(-1) is achieved at room temperature and is attributed to the formation of a crystalline phase of high lithium-ion conduction. All-solid-state lithium-ion batteries based on these glass-ceramic electrolytes are assembled by using Li2S nanoparticles or low-cost commercially available FeS2 as active cathode materials and Li-In alloys as anode. A high discharge capacity of 535 mAh g(-1) is achieved after at least 50 cycles for the all-solid-state cells with Li2S as cathode materials, suggesting a rather high capacity retention of 97.4%. Even for the cells using low-cost FeS2 as cathode materials, same high discharge capacity of 560 mAh g(-1) is also achieved after at least 50 cycles. Moreover, the Coulombic efficiency remain at ∼99% for these all-solid-state cells during the charge-discharge cycles.

  14. Recent advances in solid polymer electrolyte fuel cell technology

    SciTech Connect

    Ticianelli, E.A.; Srinivasan, S.; Gonzalez, E.R.

    1988-01-01

    With methods used to advance solid polymer electrolyte fuel cell technology, we are close to obtaining the goal of 1 A/cm/sup 2/ at 0.7. Higher power densities have been reported (2 A/cm/sup 2/ at 0.5 V) but only with high catalyst loading electrodes (2 mg/cm/sup 2/ and 4 mg/cm/sup 2/ at anode and cathode, respectively) and using a Dow membrane with a better conductivity and water retention characteristics. Work is in progress to ascertain performances of cells with Dow membrane impregnated electrodes and Dow membrane electrolytes. 5 refs., 6 figs.

  15. Variations of structures and solid-state conductivity of isomeric silver(I) coordination polymers having linear and V-shaped thiophene-centered ditriazole ligands

    SciTech Connect

    Hu, Bin; Geng, Jiao; Zhang, Lie; Huang, Wei

    2014-07-01

    A pair of new linear and V-shaped acceptor–donor–acceptor (A−D−A) thiophene-centered ditriazole structural isomers, i.e., 2,5-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 1}) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 2}), has been synthesized and characterized. They are used as μ{sub 2}-bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L{sup 1})(NO{sub 3})]{sub n} (1) and [Ag(L{sup 2})(NO{sub 3})]{sub n} (2), which are also structural isomers at the supramolecular level. X-ray single-crystal diffraction analyses for 1 and 2 reveal that they exhibit the same one-dimensional (1D) coordination polymers but different structural architectures because of the distinguishable shape and configuration of isomeric ligands (L{sup 1} and L{sup 2}) and the alterations of the coordination numbers. More interestingly, compared with the free ligands, 1D silver(I) polymeric isomers 1 and 2 show significant enhancement of solid-state conductivity to different extents (1.42×10{sup 4} and 2.17×10{sup 3} times), where 6.96 times' enhancement of solid-state conductivity from 1 to 2 has been observed. The formation of Ag–N coordinative bonds and the configurational discrepancy of L{sup 1} and L{sup 2} are believed to play important roles in facilitating the electron transport between molecules, which can also be supported by Density Function Theory calculations of their band gaps. - Graphical abstract: A pair of linear and V-shaped isomeric thiophene-centered ditriazole ligands (L{sup 1}) and L{sup 2} are used to prepare a pair of silver(I) polymeric isomers (1 and 2), where significant enhancement of solid-state conductivity to different extents are observed originating from the distinguishable shape and configuration of isomeric ligands. - Highlights: • A pair of linear and V-shaped thiophene-centered ditriazole structural isomers is prepared. • They are used as µ{sub 2}-bridging ligands to prepare a pair of silver

  16. Organic thin film transistor by using polymer electrolyte to modulate the conductivity of conjugated polymer

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Ju; Li, Yu-Chang; Yeh, Chih-Chieh; Chung, Sheng-Feng; Huang, Li-Ming; Wen, Ten-Chin; Wang, Yeong-Her

    2006-11-01

    This work presents an organic thin film transistor using double polymer layers, polymer electrolyte/conjugated polymer, i.e., poly(diallyldimethylammonium chloride) (PDDA)/poly(diphenylamine) (PDPA) structure. The single mobile anions (Cl-) pending on the PDDA are stuffed into the conjugated polymer to dope the nitrogen atoms (imine) by applying the gate bias, resulting a higher drain current under the same source-drain voltage. The PDDA/PDPA polymer structure working in the enhancement mode which operates under atmospheric conditions as a typical p-channel transistor is demonstrated.

  17. The Effect of Hsab Principle on Electrochemical Properties of Polymer-In Electrolytes with Aliphatic Polymer

    NASA Astrophysics Data System (ADS)

    Kim, Min-Kyung; Lee, Yu-Jin; Jo, Nam-Ju

    To obtain high ambient ionic conductivity of solid polymer electrolyte (SPE), we introduce polymer-in-salt system with ion hopping mechanism contrary to traditional salt-in-polymer system with segmental motion mechanism. In polymer-in-salt system, the interaction between polymer and salt is important because polymer-in-salt electrolyte contains a large amount of salt. Thus, we try to solve the origin of interaction between polymer and salt by using hard/soft acid base (HSAB) principle. The SPEs are made up of two types of polymers (poly(ethylene oxide) (PEO, hard base) and poly(ethylene imine) (PEI, softer base than PEO)) and four types of salts (LiCF3SO3 (hard cation/hard anion), LiCl (hard cation/soft anion), AgCF3SO3 (soft cation/hard anion), and AgCl (soft cation/soft anion)) according to HSAB principle. In salt-in-polymer system, ionic conductivities of SPEs were affected by HSAB principle but in polymer-in-salt system, they were influenced by the ion hopping property of salt rather than the solubility of polymer for salt according to HSAB principle. The highest ionic conductivities of PEO-based and PEI-based SPEs were 5.13 × 10-4Scm-1 and 7.32 × 10-4Scm-1 in polymer-in-salt system, respectively.

  18. Polymer electrolyte membrane assembly for fuel cells

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping S. (Inventor); Kindler, Andrew (Inventor); Yavrouian, Andre (Inventor); Halpert, Gerald (Inventor)

    2000-01-01

    An electrolyte membrane for use in a fuel cell can contain sulfonated polyphenylether sulfones. The membrane can contain a first sulfonated polyphenylether sulfone and a second sulfonated polyphenylether sulfone, wherein the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone have equivalent weights greater than about 560, and the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone also have different equivalent weights. Also, a membrane for use in a fuel cell can contain a sulfonated polyphenylether sulfone and an unsulfonated polyphenylether sulfone. Methods for manufacturing a membrane electrode assemblies for use in fuel cells can include roughening a membrane surface. Electrodes and methods for fabricating such electrodes for use in a chemical fuel cell can include sintering an electrode. Such membranes and electrodes can be assembled into chemical fuel cells.

  19. Polymer electrolyte membrane assembly for fuel cells

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping S. (Inventor); Kindler, Andrew (Inventor); Yavrouian, Andre (Inventor); Halpert, Gerald (Inventor)

    2002-01-01

    An electrolyte membrane for use in a fuel cell can contain sulfonated polyphenylether sulfones. The membrane can contain a first sulfonated polyphenylether sulfone and a second sulfonated polyphenylether sulfone, wherein the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone have equivalent weights greater than about 560, and the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone also have different equivalent weights. Also, a membrane for use in a fuel cell can contain a sulfonated polyphenylether sulfone and an unsulfonated polyphenylether sulfone. Methods for manufacturing a membrane electrode assemblies for use in fuel cells can include roughening a membrane surface. Electrodes and methods for fabricating such electrodes for use in a chemical fuel cell can include sintering an electrode. Such membranes and electrodes can be assembled into chemical fuel cells.

  20. Electrochromic cells with lutetium diphthalocyanine and semisolid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Pizzarello, F. A.; Nicholson, M. M.

    1987-11-01

    Cyclic voltammograms were obtained for lutetium diphthalocyanine films in contact with plasticized poly(ethylene oxide) (PEO) electrolytes or solvent-swollen 2-acrylamido-2-methylpropane- sulfonic acid (AMPS) polymer electrolytes. Cells containing PEO-salt combinations plasticized with propylene glycol (PG) or acetonitrile resulted in slow, nonuniform color changes due to high interfacial resistance. The AMPS cell fabrication was simplified by starting with a commercial AMPS polymer product in the form of a transparent sheet containing water and other additives. This material, when further swollen in a PG-HC1 solution, produced the full range of uniform colors, accompanied by well defined voltammograms. It maintained good contact with the dye from -5 to 40 C.

  1. Composite polymer electrolyte for Li-ion battery

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Xu, Fan; Cheng, Yan; Jiang, Zhiyu

    2002-06-01

    A new method presented in this work mainly describes how to produce polymer electrolyte membranes by using water as plasticizer. Compared with the membranes made by traditional methods, the membranes made by the new method have the properties of easy handling and free-standing. The results of Ac impedance suggest that the polymer electrolyte membranes have high ionic conductivity. Moreover, the images of SEM show that the porous and alveolate structures are greatly improved. It is more important that using water as plasticizer can lower the cost of producing Li-ion batteries and eliminate the pollution produced in process of plasticizer extraction, in which some volatile solvents were used in traditional methods.

  2. Electrochromic Li sub x WO sub 3 /polymer laminate/Li sub y V sub 2 O sub 5 device: toward an all-solid-state smart window

    SciTech Connect

    Andersson, A.M.; Granqvist, C.G. ); Stevens, J.

    1989-08-15

    We introduce a laminate two-layer approach to electrochromic smart windows. It incorporates two glass panes, each having a two-layer coating, laminated by a transparent adhesive solid polymer electrolyte. Each coating has a transparent conducting base layer (In{sub 2}O{sub 3}:Sn) and a top layer of an ion-insertion compound (based on WO{sub 3} or V{sub 2}O{sub 5}). The layers were made by evaporation or sputtering. Cyclic voltammetry in liquid electrolytes and spectrophotometry were used to characterize the layers. A novel electrolyte was developed: it comprised a methyl methacrylate network incorporating poly(propylene glycol) complexed with lithium perchlorate. Initial optical data are reported for laminated devices having an active electrochromic Li{sub {ital x}}WO{sub 3} layer and a passive Li{sub {ital y}}V{sub 2}O{sub 5} counter electrode.

  3. Solid state electrochemical current source

    DOEpatents

    Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

    2002-04-30

    A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

  4. Structure, morphology and ionic conductivity of solid polymer electrolyte

    SciTech Connect

    Dey, Arup; Karan, S.; Dey, Ashis; De, S.K.

    2011-11-15

    Graphical abstract: Two-dimensional atomic force image of pure polyethylene oxide presents a crystallized network of regular spherulites developing spirals and branches of well distributed surface contours. Highlights: {yields} The incorporation of ceria significantly modifies the morphology of polyethylene oxide (PEO)-KI complex. {yields} The ionic conductivity increases by about two orders of magnitude by the addition of ceria nanoparticles. {yields} Ionic conductivity as a function of ceria concentration reveals two maxima. {yields} Grain boundary effect of nanofiller, strong Lewis acid-base interaction between PEO and nanosized ceria, change of conformation of PEO molecule and epitaxial effect of ceria nanoparticles control the ionic conductivity of composite polymer electrolyte. -- Abstract: Polyethylene oxide (PEO) complexed with potassium iodide (KI) is synthesized to investigate the ionic conductivity of alkaline based polymer electrolytes. The structural and morphological characterizations of the nanocomposite polymer electrolytes are performed by X-ray diffractometry (XRD), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) measurements. The ionic conductivity increases with the increase of KI concentration up to about 20 wt.%. The effect of nanosized ceria (CeO{sub 2} {approx} 10 nm) fillers on ionic conductivity in PEO-KI polymer electrolyte is also carried out, keeping PEO to KI wt.% ratio 80:20 and 85:15. The result reveals that the addition of ceria nanoparticles enhances the conductivity by two orders of magnitude. The presence of ceria at the highest concentration induces the same molecular environment within PEO chain as that of undoped PEO. Temperature dependence of ionic conductivity follows Arrhenius mechanism.

  5. Solid-state proton conductors

    NASA Astrophysics Data System (ADS)

    Jewulski, J. R.; Osif, T. L.; Remick, R. J.

    1990-12-01

    The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling, and optimization studies. Correlation and optimization studies are described which include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells are presented which include the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms.

  6. Solid-state proton conductors

    SciTech Connect

    Jewulski, J.R.; Osif, T.L.; Remick, R.J.

    1990-12-01

    The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling and optimization studies. Correlation and optimization studies, to include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells including the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms. 164 refs., 27 figs., 13 tabs.

  7. Suppression of Lithium Dendrite Formation by Using LAGP-PEO (LiTFSI) Composite Solid Electrolyte and Lithium Metal Anode Modified by PEO (LiTFSI) in All-Solid-State Lithium Batteries.

    PubMed

    Wang, Chunhua; Yang, Yifu; Liu, Xingjiang; Zhong, Hai; Xu, Han; Xu, Zhibin; Shao, Huixia; Ding, Fei

    2017-04-07

    The formation of lithium dendrites is suppressed using a Li1.5Al0.5Ge1.5(PO4)3-poly(ethylene oxide) (LAGP-PEO) composite solid electrolyte and a PEO (lithium bis(trifluoromethane)sulfonimide) [PEO (LiTFSI)]-modified lithium metal anode in all-solid-state lithium batteries. The effects on the anode performance based on the PEO content in the composite solid electrolyte and the molecular weight of PEO used to modify the Li anode are studied. The structure, surface morphology, and stability of the composite solid electrolyte are examined by X-ray diffraction spectroscopy, scanning electron microscopy, and electrochemical tests. Results show that the presence of a PEO-500000(LiTFSI) film on a Li anode results in good mechanical properties and satisfactory interface contact features. The film can also prevent Li from reacting with LAGP. Furthermore, the formation of lithium dendrites can be effectively inhibited as the composite solid electrolyte is combined with the PEO film on the Li anode. The ratio of PEO in the composite solid electrolyte can be reduced to a low level of 1 wt %. PEO remains stable even at a high potential of 5.12 V (vs Li/Li(+)). The assembled Li-PEO (LiTFSI)/LAGP-PEO/LiMn0.8Fe0.2PO4 all-solid-state cell can deliver an initial discharge capacity of 160.8 mAh g(-1) and exhibit good cycling stability and rate performance at 50 °C.

  8. A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized β-polytype porous silicon carbide electrodes.

    PubMed

    Kim, Myeongjin; Yoo, Jeeyoung; Kim, Jooheon

    2017-05-23

    A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo2O4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo2O4) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g(-1) at a scan rate of 5 mV s(-1) in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe3O4 nanoparticles and SiCF (SiCF/Fe3O4) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g(-1) at a scan rate of 5 mV s(-1). Therefore, by pairing the SiCF/MgCo2O4 positive electrode and the SiCF/Fe3O4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g(-1) at a scan rate of 5 mV s(-1)) and energy density (maximum energy density of 72.79 Wh kg(-1) at a power density of 727.96 W kg(-1)).

  9. Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR.

    PubMed

    Abraham, Anuji; Crull, George

    2014-10-06

    A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.

  10. Synthesis and characterization of aminated perfluoro polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Page-Belknap, Zachary Stephan Glenn

    Polymer electrolytes have been developed for use in anion exchange membrane fuel cells for years. However, due to the highly corrosive environment within these fuel cells, poor chemical stability of the polymers and low ion conductivity have led to high development costs and thus prevention from widespread commercialization. The work in this study aims to provide a solution to these problems through the synthesis and characterization of a novel polymer electrolyte. The 800 EW 3M PFSA sulfonyl fluoride precursor was aminated with 3-(dimethylamino)-1-propylamine to yield a functional polymer electrolyte following quaternization, referred to in this work as PFSa-PTMa. 1 M solutions of LiPF6, HCL, KOH, NaOH, CsOH, NaHCO3 and Na2CO3 were used to exchange the polymer to alternate counterion forms. Chemical structure analysis was performed using both FT and ATR infrared spectroscopy to confirm sulfonyl fluoride replacement and the absence of sulfonic acid sites. Mechanical testing of the polymer, following counterion exchange with KOH, at saturated conditions and 60 ºC exhibited a tensile strength of 13 +/- 2.0 MPa, a Young's modulus of 87 +/- 16 MPa and a degree of elongation reaching 75% +/- 9.1%, which indicated no mechanical degradation following exposure to a highly basic environment. Conductivities of the polymer in the Cl- and OH- counterion forms at saturated conditions and 90 ºC were observed at 26 +/- 8.0 mS cm-1 and 1.1 +/- 0.1 mS cm-1, respectively. OH- conductivities were slightly above those observed for CO32- and HCO 3- counterions at the same conditions, 0.63 +/- 0.18 and 0.66 +/- 0.21 mS cm-1 respectively. The ion exchange capacity (IEC) of the polymer in the Cl- counterion form was measured via titration at 0.57 meq g-1 which correlated to 11.2 +/- 0.10 water molecules per ion site when at 60ºC and 95% relative humidity. The IEC of the polymer in the OH- counterion form following titration expressed nearly negligible charge density, less than 0.01 meq

  11. Photocured PEO-based solid polymer electrolyte and its application to lithium-polymer batteries

    NASA Astrophysics Data System (ADS)

    Kang, Yongku; Kim, Hee Jung; Kim, Eunkyoung; Oh, Bookeun; Cho, Jae Hyun

    A solid polymer electrolyte (SPE) based on polyethylene oxide (PEO) is prepared by photocuring of polyethylene glycol acrylates. The conductivity is greatly enhanced by adding low molecular weight poly(ethylene glycol) dimethylether (PEGDME). The maximum conducticity is 5.1×10 -4 S cm -1 at 30°C. These electrolytes display oxidation stability up to 4.5 V against a lithium reference electrode. Reversible electrochemical plating/stripping of lithium is observed on a stainless steel electrode. Li/SPE/LiMn 2O 4 as well as C(Li)/SPE/LiCoO 2 cells have been fabricated and tested to demonstrate the applicability of the resulting polymer electrolytes in lithium-polymer batteries.

  12. Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

    2002-01-01

    Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

  13. High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO2 Nanospheres in Poly(ethylene oxide).

    PubMed

    Lin, Dingchang; Liu, Wei; Liu, Yayuan; Lee, Hye Ryoung; Hsu, Po-Chun; Liu, Kai; Cui, Yi

    2016-01-13

    High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer-ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO2 nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO4 dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10(-3) S cm(-1) at 60 °C, 4.4 × 10(-5) S cm(-1) at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

  14. Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries

    DOE PAGES

    Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.; ...

    2016-03-31

    Fluorinated carbonate solvents are pursued as liquid electrolytes for high-voltage Li-ion batteries. We report aggregation of [Li+(FEC)3]n polymer species from fluoroethylene carbonate containing electrolytes and scrutinized the causes for this behavior.

  15. Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries.

    PubMed

    Malliakas, Christos D; Leung, Kevin; Pupek, Krzysztof Z; Shkrob, Ilya A; Abraham, Daniel P

    2016-04-28

    Fluorinated carbonates are pursued as liquid electrolyte solvents for high-voltage Li-ion batteries. Here we report aggregation of [Li(+)(FEC)3]n polymer species in fluoroethylene carbonate containing electrolytes and scrutinize the causes for this behavior.

  16. Spontaneous Aggregation of Lithium Ion Coordination Polymers in Fluorinated Electrolytes for High-Voltage Batteries

    SciTech Connect

    Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.; Shkrob, Ilya A.; Abraham, Daniel P

    2016-04-28

    Fluorinated carbonates are pursued as liquid electrolyte solvents for high-voltage Li-ion batteries. Here we report aggregation of [Li+(FEC)(3)](n) polymer species in fluoroethylene carbonate containing electrolytes and scrutinize the causes for this behavior.

  17. Physical properties of Li ion conducting polyphosphazene based polymer electrolytes

    SciTech Connect

    Sanderson, S.; Zawodzinski, T.; Hermes, R.; Davey, J.; Dai, Hongli

    1996-12-31

    We report a systematic study of the transport properties and the underlying physical chemistry of some polyphosphazene (PPhz)-based polymer electrolytes. We synthesized MEEP and variants which employed mixed combinations of different length oxyethylene side-chains. We compare the conductivity and ion-ion interactions in polymer electrolytes obtained with lithium triflate and lithium bis(trifluoromethanesulfonyl)imide (TFSI) salts added to the polymer. The combination of the lithium imide salt and MEEP yields a maximum conductivity of 8 x 10{sup -5} {Omega}{sup -1} cm{sup -1} at room temperature at a salt loading of 8 monomers per lithium. In one of the mixed side-chain variations, a maximum conductivity of 2 x 10{sup -4} {Omega}{sup -1} cm{sup -1} was measured at the same molar ratio. Raman spectral analysis shows some ion aggregation and some polymer - ion interactions in the PPhz-LiTFSI case but much less than observed with Li CF{sub 3}SO{sub 3}. A sharp increase in the Tg as salt is added corresponds to concentrations above which the conductivity significantly decreases and ion associations appear.

  18. Computationally Guided Design of Polymer Electrolytes for Battery Applications

    NASA Astrophysics Data System (ADS)

    Wang, Zhen-Gang; Webb, Michael; Savoie, Brett; Miller, Thomas

    We develop an efficient computational framework for guiding the design of polymer electrolytes for Li battery applications. Short-times molecular dynamics (MD) simulations are employed to identify key structural and dynamic features in the solvation and motion of Li ions, such as the structure of the solvation shells, the spatial distribution of solvation sites, and the polymer segmental mobility. Comparative studies on six polyester-based polymers and polyethylene oxide (PEO) yield good agreement with experimental data on the ion conductivities, and reveal significant differences in the ion diffusion mechanism between PEO and the polyesters. The molecular insights from the MD simulations are used to build a chemically specific coarse-grained model in the spirit of the dynamic bond percolation model of Druger, Ratner and Nitzan. We apply this coarse-grained model to characterize Li ion diffusion in several existing and yet-to-be synthesized polyethers that differ by oxygen content and backbone stiffness. Good agreement is obtained between the predictions of the coarse-grained model and long-timescale atomistic MD simulations, thus providing validation of the model. Our study predicts higher Li ion diffusivity in poly(trimethylene oxide-alt-ethylene oxide) than in PEO. These results demonstrate the potential of this computational framework for rapid screening of new polymer electrolytes based on ion diffusivity.

  19. Fabrication of a polymer battery based on polypyrrole electrodes and a polymer gel electrolyte

    SciTech Connect

    Killian, J.G.; Coffey, B.M.; Poehler, T.O.; Searson, P.C.

    1995-12-31

    The electronic conductivity and redox behavior of conjugated polymers make them suitable for charge storage applications. The authors present preliminary results for an all polymer system consisting of a p-doped polypyrrole cathode and pseudo n-doped polypyrrole/polystyrenesulfonate anode. Using a thin film construction technique, electrodes were assembled into cells using a polymer gel electrolyte based on polyacrylonitrile, which has a high room temperature conductivity. Charge capacities of 13 mAh g{sup {minus}1} based on the mass of the electroactive polymer in the cathode have been obtained for over 100 cycles.

  20. Direct probing of a polymer electrolyte/luminescent conjugated polymer mixed ionic/electronic conductor.

    PubMed

    Hu, Yufeng; Gao, Jun

    2009-12-30

    What will happen if one brings two metallic probes into direct contact with a polymer film and apply a voltage bias? We demonstrate that, for a mixed ionic/electronic conductor containing a luminescent conjugated polymer and a polymer electrolyte, it is possible to induce strong in situ electrochemical doping of the luminescent polymer and form a dynamic light-emitting p-n junction. Using time-lapse fluorescence imaging, we have visualized p- and n-doping of various shapes and shades, p-n junction electroluminescence, and the effects of voltage reversal. The direct probing technique offers great simplicity and versatility for studying luminescent mixed ionic/electronic conductors.