Steve Harris, Lawrence Berkeley National Laboratory
Ping Liu, Advanced Research Projects Agency-Energy (ARPA-E)
Jie Xiao, Pacific Northwest National Laboratory
Yan Yao, University of Houston
LL2: Solid State Electrolyte
Monday PM, November 30, 2015
Hynes, Level 3, Room 309
2:30 AM - *LL2.01
All-Solid-State Li-Ion Batteries for Transformational Energy Storage
Eric David Wachsman 1 Gregory Hitz 1 Dennis Wayne McOwen 1 Yang Wen 1 Yunhui Gong 1 Xiaogang Han 1 Kun Fu 1 Huili Liu 1 Liangbing Hu 1 Chunsheng Wang 1 Venkataraman Thangadurai 2
1University of Maryland College Park United States2University of Calgary Calgary CanadaShow Abstract
We have developed transformational, and intrinsically safe, all-solid-state Li-ion batteries (SSLiBs), by incorporating high conductivity garnet-type solid Li-ion electrolytes into tailored tri-layer microstructures, by low-cost solid oxide fuel cell (SOFC) fabrication techniques to form electrode supported dense thin-film (~10mu;m) solid-state electrolytes. The microstrucurally tailored porous garnet scaffold support increases electrode/electrolyte interfacial area, overcoming the high impedance typical of planar geometry SSLiBs resulting in an area specific resistance (ASR) of only ~2 Omega;cm-2 at room temperature. The unique garnet scaffold/electrolyte/scaffold structure further allows for charge/discharge of the Li-metal anode and cathode scaffolds by pore-filling, thus providing high depth of discharge ability without mechanical cycling fatigue seen with typical electrodes. Moreover, these scalable multilayer ceramic fabrication techniques, without need for dry rooms or vacuum equipment, provide for dramatically reduced manufacturing cost.
Fabrication of supported dense thin-film garnet electrolytes, their ability to cycle Li-metal at high current densities with no dendrite formation, and results for Li-metal anode/garnet-electrolyte based batteries with a number of different cathode chemistries will be presented.
3:00 AM - *LL2.02
All-Solid-State and Aqueous Li-Ion Batteries
Chunsheng Wang 1 Kang Xu 2 Fudong Han 1 Liumin Suo 1
1Univ of Maryland College Park United States2Army Research Lab Adelphi United StatesShow Abstract
Safe Li-ion battery is critical for success of electric vehicle, and the electrolytes are one of the most important component for the safety of the Li-ion batteries. In this talk, we summarize the research progress of our group on all-solid-state Li-ion batteries and aqueous Li-ion batteries. In all-solid-state Li-ion battery, we report a novel concept of a single-material all-solid-state lithium-ion battery, wherein a single Li10GeP2S12 serves as an electrolyte, an anode, and a cathode, to eliminate the highly resistive interface between the electrodes and electrolyte. The realization of the single-Li10GeP2S12 battery is based on the fact that the Li-S and Ge-S components in Li10GeP2S12 could act as the active centers for lithiation/delithiation as a cathode and an anode, respectively, when electronically-conductive carbon is mixed, while pure Li10GeP2S12 can be used as an electrolyte. This unique concept of a single-material lithium-ion battery can be extended to other solid-state battery systems, providing a new direction for high-power, high-energy, long-cycling solid-state batteries. For aqueous Li-ion battery, we report a new aqueous electrolyte, whose electrochemical stability window was expanded to ~3.0 V. A full Li-ion battery of 2.0 V was demonstrated to cycle over 1000 times in this electrolyte, with nearly 100% Coulombic efficiency at both low (0.15 C) and high (4.5 C) rates.
4:00 AM - LL2.03
3D Printing Solid-State Li-Ion Batteries
Dennis Wayne McOwen 1 Gregory Hitz 1 Tanner Hamann 1 Eric David Wachsman 1
1University of Maryland Energy Research Center College Park United StatesShow Abstract
Over the last decade, Li-ion batteries have begun to dominate several energy storage markets due to the many inherent advantages of Li-ion chemistry. More recently, a new approach to Li-ion battery technology has been investigated—utilizing solid-state electrolytes made of lithium garnet-type ceramics. (e.g. Li7La3Zr2O12 or LLZ) These materials are inherently non-flammable and contain no toxic or reactive fluorine. Importantly, garnet materials like LLZ are electrochemically stable to Li metal (enabling higher energy density batteries), and are also thermally stable and mechanically strong. The main areas challenging the development of all-solid-state Li-ion batteries, however, have been low ionic conductivity and high interfacial impedance due, in part, to poor solid-solid contact. The ionic conductivity of garnet materials has been steadily increasing as new compositions/dopants are discovered and sintering conditions are optimized. However, if a method existed which could provide precise control over the microstructure, both of the issues could be resolved. First, the thickness of the electrolyte separating the two electrodes could be reduced to the order of tens of microns, such that the overall resistance of the bulk electrolyte would become negligible. Secondly, by tailoring the architecture of the contact surface of the electrolyte with the electrode, the interfacial impedance could be similarly reduced.
With the recent growth and maturation of 3D printing, such precise control over microstructure is now possible, both for scientific and technical applications. Using a 3D printer armed with devices such as a UV lamp for photopolymer spot curing and a laser for laser sintering, not only can the microstructure of the solid electrolyte be adequately controlled, but the interface with the anode and cathode can be modified as well. This presents a distinctive way of quickly fabricating unique, ordered architectures to address the impedance issues described above. Using a 3D printer, thin solid-state batteries have been printed using different microstructures/architectures for each component to explore the effect of each on battery properties. For example, the aspect ratio has been found to significantly impact the performance metrics. Additionally, using characterization tools such as electrochemical impedance spectroscopy, Raman spectroscopy, and SEM, bulk properties and interfacial effects can be investigated with a high degree of accuracy. In this way, both macro and microscopic spatial variations of structure and composition will be probed.
4:15 AM - LL2.04
Investigation of a Polymer Electrolyte/Cathode Interface in a Solid-State Lithium Battery
Matthew D. Widstrom 2 Arthur Von Wald Cresce 1 Peter Kofinas 3 2
1US Army Research Lab Adelphi United States2University of Maryland College Park College Park United States3University of Maryland College Park College Park United StatesShow Abstract
Solid polymer electrolytes (SPEs) possess an inherent safety advantage over traditional liquid carbonate electrolytes, and can be incorporated into an effective solid-state battery at physiological temperature for use in implantable devices. In this work, we report on our progress towards the goal of the development of a solid-state battery utilizing a SPE. The electrochemical properties of a SPE using a poly(ethylene oxide) (PEO) polymer matrix in the presence of tri-ethyl sulfonium bis(trifluorosulfonyl) imide (S2TFSI) ionic liquid (IL) and lithium TFSI with appreciable ionic conductivity ~ 1 mS/cm at physiological temperature are presented. These homogenous, mechanically robust films were fabricated via a hot-pressing method and incorporated into lithium metal/SPE/lithium cobalt oxide or lithium iron phosphate pouch cells where the cycling performance and rate capability were assessed. The cells were disassembled post-mortem and the SPE/cathode interface was examined using a dual FIB-SEM system whereby FIB was used to expose fresh SPE/cathode interface and SEM was used for imaging and elemental composition analysis.
4:30 AM - *LL2.05
Biomimetic Solid Electrolyte
Yunfeng Lu 1
1UCLA Los Angeles United StatesShow Abstract
Lithium-ion batteries (LIBs) are one of the most widely used energy storage devices in modern society, and they are playing important roles in the rapidly developing markets of pure/hybrid electric vehicles and other large-scale energy storage systems. Current LIBs utilize flammable liquid electrolytes, which have brought potential risks, especially for large-scale applications. Moreover, additional problems emerge when moving to advanced systems beyond conventional LIBs, such as lithium-sulfur and lithium-air batteries, where the use of metallic lithium as anode would cause dendrite formation and raise safety concerns regarding short circuit. Solid electrolytes have been considered as feasible solutions to the safety issues of liquid ones.
Continuous efforts have been devoted in the past few decades to search new materials for solid electrolytes, which mainly include ceramic-based and polymer-based electrolytes. In this work, a novel class of solid electrolytes with biomimetic ionic channels will be discussed, providing a new direction towards high-performance and robust LIBs.
5:00 AM - LL2.06
Innovative Alumina Nanofluid-Based Electrolyte for Thermo-Electrochemical Cells
Chang Liu 1 Shien Ping Feng 1
1The University of Hong Kong Hong Kong ChinaShow Abstract
Thermo-electrochemical cells with aqueous electrolyte that convert low-grade heat (<130 degree Centigrade) directly into electrical energy, has attracted considerable attentions as an alternative strategy to thermal energy harvesting. However, innately poor electrical conductivity of aqueous ferro/ferricyanide electrolyte is one of critical factors to limit the efficiency of thermal-electrochemical cells. In order to enhance electrical conductivity and diffusivity of the electrolyte, applying nanoparticles into the electrolyte which is called electrolyte-based nanofluids can be one of promising ways for the augmentation of mass transport in the electrolyte through the combined effect of percolation behavior and convection. The presence of nanoparticles in electrolyte is seldom studied due to intrinsic instability of nanofluids, especially, in electrolyte with high ionic strength. Moreover, the collocation of base fluids and nanoparticles are strictly restricted by both chemical and physical properties for a stable nanoparticles suspension. Here we report a practicable approach fabricating γ-alumina nanofluid-based ferro/ferricyanide electrolyte equipped with enhanced electrical conductivity and feasible stability by introducing stirred nano-bead milling in conjunction with ultrasonication. Sodium dodecyl sulfate is introduced to stabilize alumina nanoparticles in ferro/ferricyanide electrolyte by constructing steric barriers. 0.2M alumina nanofluid-based ferro/ferricyanide electrolyte holds an ionic concentration 20-fold higher than previous work in the literature, providing practical significance to develop nanofluid-based electrolyte for thermo-electrochemical cells. Based on electrical conductivity and rotating disk electrode studies, the diffusivity of alumina nanofluid-based electrolyte at a nanoparticle mass fraction of 0.25% shows a mutative response to convection, revealing a critical deviation from homogeneous standard ferro/ferricyanide electrolyte at high angular velocities. We decipher this conspicuous increase of the limiting current as a result of both percolation behavior and convection under shear flow. Additionally, alumina nanofluid-based electrolyte is confined by relatively high viscosity, which counteracts to the thermal conductivity. 0.2M alumina nanofluid-based ferro/ferricyanide is demonstrated in thermo-electrochemical cells to capture a progressive figure of merit of 29.9×10-6K-1.
5:15 AM - LL2.07
Surface Oxygen Exchange Kinetics for Solid-Oxide-Electrolyte Metal-Air Batteries
Gil Cohn 1 Jie Wang 2 Kevin Huang 2 Eric D. Wachsman 1
1University of Maryland College Park United States2University of South Carolina Columbia United StatesShow Abstract
A new type of all-solid-state metal-air battery is being developed by the University of South Carolina, based on a reversible solid oxide fuel cell. The operation of this metal-air battery is based on Oshy;2- conduction, and is able to provide high specific energy and high round-trip efficiency at a temperature as low as 550oC. However, operation at temperature lower than 550oC requires a new class of high conductivity catalytic oxide-ion electrolyte. For that propose, a new cobalt-based perovskite oxide with high catalytic activity for oxygen reduction was developed.
Here we report on the surface exchange properties of that new material, SrCo0.9-xNb0.1FexO3-δ, by means of in-situ oxygen isotope exchange. We used our unique heterogeneous catalysis system to determine the oxygen exchange rate coefficients and mechanism for a variety of Fe doping concentrations. Oxygen exchange profiles indicate an enhanced exchange properties of SrCo0.9Nb0.1O3-δ over the other Fe concentrations. Exchange of 18O2 reaches a saturation at 450-500oC, while below 300oC the exchange is very slow. Fitting the exchange results to a model describing the exchange process we were able to extract the temperature dependence of the exchange coefficient as well as the activation energy for oxygen exchange and compared with the literature data. Reaction order, together with the identity of the oxygen species taking part in the reaction are also investigated through variation in the oxygen partial pressure. The results explicity show an extensive oxygen exchange abiltiy of the electrolyte at intermidiate temperatures.
LL3: Poster Session I
Monday PM, November 30, 2015
Hynes, Level 1, Hall B
9:00 AM - LL3.01
Development of a Flexible High Potential Thin Film Zinc-Air Battery by Screen Printing Technique
Sira Suren 1 Soorathep Kheawhom 1
1Chulalongkorn Univ Bangkok ThailandShow Abstract
This work investigates the development of a flexible high potential thin film zinc-air battery by screen printing technique. Commercial Ag ink was used as the anode and cathode current collectors. Polypropylene membrane was used as the separator. 9 M KOH was used as the electrolyte. Mixture of Zn powder, ZnO, and Bi2O3 was used as the anode electrode. Types of cathode active materials (carbon paper and carbon black) were investigated. Results showed that batteries using carbon paper and carbon black as active materials provided the open-circuit voltage at 1.44 and 1.45 V, respectively. When batteries were discharged at 0.15 mA/cm2, the open-circuit voltage observed from both batteries using carbon paper and carbon black as the active materials were 1.23 V. Battery using carbon black showed a little longer discharging time. Energy density observed from battery using carbon black was 682 Wh kg-1 and that using carbon paper was 323 Wh kg-1.
9:00 AM - LL3.02
Transparent Thin Film Cathode Electrode for Zn-MnO2 Battery Fabrication
Sira Suren 1 Thanatham Julaphatachote 1 Soorathep Kheawhom 1
1Chulalongkorn Univ Bangkok ThailandShow Abstract
Transparent cathode electrode has been successfully fabricated with microelectrode array pattern using screen printing technique. The result from UV/Vis spectra between 400 to 800 nm indicated that battery with an electrode area of 25 percent (battery A) had transparency of 82 percent, while battery with an electrode area of 20 percent (battery B) had transparency of 86 percent. It can be concluded that transparency of the electrode is inversely proportional to the electrode area percentage. Potentiostat was used to determine the prototype batteries performances. Both battery A and battery B provided the same open-circuit voltage at 1.3 V indicating that the electrode area percentage had no effect on the open-circuit voltage. Both batteries had similar shape of current-voltage characteristic, however, battery A had a flatter slope in the Ohmic polarization region compare with battery B, indicating that battery A could provide more stable current at a given voltage. This was due to higher contact area between the microelectrode array and the electrolyte of the battery A than that of battery B. Nevertheless, further optimization of the battery is still needed in order to make it applicable to be functioned as a transparent energy source for transparent device.
9:00 AM - LL3.03
Single Walled Carbon Nanotube - Cobalt Oxide Nanocomposites as Supercapacitor Electrode Materials
Mete Batuhan Durukan 1 Recep Yuksel 2 Husnu Emrah Unalan 1
1Middle East Technical University Ankara Turkey2Middle East Technical University Ankara TurkeyShow Abstract
While the double-layered supercapacitors that use carbon materials with high surface areas are commercialized; metal oxide active materials has attracted much more attention in recent years. This is because of their pseudocapacitive behavior; high redox activity and high reversibility. Cobalt oxides (Co3O4 and CoOx) are reported to have high pseudocapacitive properties, which make them promising electrode materials for supercapacitors. Hybrid capacitors using multi-walled carbon nanotubes and cobalt oxides are reported to have high capacitance values; however, research on electrodeposition of cobalt oxide onto single walled carbon nanotube thin films and supercapacitors fabricated by this means with a low-cost route remained elusive.
In this work, single walled carbon nanotube (SWNT) and cobalt oxide hybrid electrodes were prepared and tested. SWNT thin films were fabricated via a low-cost vacuum filtration and consecutive stamping method onto glass substrates and cobalt oxides were electrodeposited from a cobalt nitrate solution. Co3O4 phase is obtained by annealing the as- electrodeposited specimen. The capacitive behavior of the hybrid supercapacitors was investigated through cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy. The total charge transfer and Faraday&’s Law were used to obtain the amount of electrodeposited cobalt oxide. A specific capacitance of 230 F/g was obtained at a scan rate of 1 mV/s for the hybrid electrodes. A detailed analysis on the capacitive behavior will be presented in conjunction with the oxidation states and morphology of the active materials.
9:00 AM - LL3.04
Single Walled Carbon Nanotube - Conducting Polymer Electrodes for Electrochromic Supercapacitors
Recep Yuksel 2 Ali Cirpan 3 Husnu Emrah Unalan 1
1Middle East Technical University Ankara Turkey2Middle East Technical University Ankara Turkey3Middle East Technical University Ankara TurkeyShow Abstract
Supercapacitor devices are complementing batteries with their high power and moderate energy densities. There are commercial batteries that show the remaining battery power through a gauge by means of a thermochromic indicator that measures the heat resistance. Likewise, what if the supercapacitors are made to reveal their stored capacity? One could use electrochromic polymeric materials for this purpose to reflect the stored capacity via color change. A new benzotriazole (BTz) and dithienothiophene (DTT) containing conducting polymer (CP) is emerged as a promising active material both for its electrochromic and electrochemical properties combined in a single device. In this work, we report on the fabrication and characterization of supercapacitors with single walled carbon nanotube (SWNT) and new CP network electrodes. Vacuum filtered SWNT thin films in this work provided high surface area, high conductivity and high transparency for the electrochromic polymer. CP was deposited onto SWNT thin films by drop-casting and experienced multiple color changes with respect to its charged state. Specific capacitance of SWNT/CP nanocomposite electrodes was obtained to be 112 F/g, which was higher than that of bare SWNT electrodes. We will present a detailed analysis of the electrochromic and electrochemical properties of the fabricated supercapacitor electrodes.
9:00 AM - LL3.05
The Bulwark of Multiple Surface Modifications to Revive the Recycled Waste for Si-Based Lithium Ion Battery
Bing-Hong Chen 1 Shang-I Chuang 1 Jenq-Gong Duh 1 Hao Yang 1
1National Tsing Hua University Hsinchu TaiwanShow Abstract
Unlike the conventional manufacturing to synthesize nano-silicon with special morphology for lithium ion battery, the peculiar anode material was extracted from the wastes of solar cell industries, which is oversize in micro scale with irregular morphology. Instead of most efforts to avoid the volume expansion, this study demonstrates a multiple surface modifications of atmospheric pressure plasma and carbon overlayer to build a bulwark between electrode and electrode. With different combination of surface modification, the surface chemical bonds of electrode and carbon overlayer were rearranged and nitrogen were revealed to be doped onto the electrode material through the examination of XPS. Raman spectroscope was adopted to verify the ratio of order and disorder of carbon overlayer with/without plasma treatment. The distinct bulwark was formed on the surface which have the function to mitigate the sever formation of solid electrolyte interface (SEI). The enhanced performance was examined between voltage window of 0.05 and 1.2 V with stable retention and high Coulombic efficiency. Through the analysis of cyclic voltammetry and AC impedance, the electrochemical properties were evaluated with the insertion/extraction behavior and internal circuit resistances. Furthermore, the etching profile of XPS interpreted the difference in multiple surface modifications, and provided the evidence of the bulwark after first cycling. Finally, the combination of plasma treatment and carbon layer gives the waste with a new life for potential application.
9:00 AM - LL3.06
Synthetic Control of Composition and Crystallite Size of Silver Ferrite Composites: Profound Electrochemical Impacts
Jessica Durham 1 Kevin Kirshenbaum 2 Amy Marschilok 1 Esther Sans Takeuchi 1 2 Kenneth Takeuchi 1
1Stony Brook Univ Stony Brook United States2Brookhaven National Laboratory Upton United StatesShow Abstract
Silver ferrite, AgFeO2, exhibits a layered delafossite-type structure with the general chemical formula ABO2. A low-temperature, aqueous co-precipitation reaction employing non-stoichiometric ratios of starting materials, AgNO3 and Fe(NO3)3, was developed allowing for the manipulation of composition (AgxFeO2, 0.2 le; x le; 1.0) and crystallite size (10-18 nm). The composite nature of the low silver materials as a combination of crystalline silver ferrite, AgFeO2, and non-crystalline maghemite, γ-Fe2O3, was established by Raman spectroscopic and X-ray absorption analyses. The layered structure of delafossites enables ion transport and a limited number of literature reports describe exploration of silver delafossite oxides as cathodes in lithium-based batteries, including an investigation of AgCuO2 and AgCu0.5Mn0.5O2. Studies of AgFeO2 demonstrated that stoichiometric silver ferrite, with an Ag : Fe ratio of 1 : 1 and an average crystallite size of 31 nm, is electrochemically active. As a cathode, the low silver content composites (x = 0.2) exhibited significantly enhanced electrochemical performance with capacities approximately100% higher relative to stoichiometric AgFeO2 and demonstrated the lowest capacity fade. The synthetic approach demonstrated herein provides a new paradigm for composite synthesis, offers an economically feasible method to prepare electrode materials, and is applicable for industrial scales. This research can be applied to viable electrode materials to increase the efficacy and energy density of modern battery technologies.
9:00 AM - LL3.07
Progress towards High-Power Li/CFx Batteries: Electrode Architectures Using Carbon Nanotubes with CFx
Qing Zhang 1 Kenneth Takeuchi 1 Esther Sans Takeuchi 1 2 Amy Marschilok 1
1Stony Brook Univ Stony Brook United States2Brookhaven National Laboratory Upton United StatesShow Abstract
The lithium-carbon monofluoride (Li/CFx) battery system exhibits desirable battery characteristics of high energy density (exceeding 2000 Wh/kg), long shelf-life, and low self-discharge. These batteries have been utilized in a wide range of applications including implantable medical devices, portable communication devices, and military and aerospace electronics. However, the broader application of Li/CFx batteries has been limited by their power capability. Multi-walled carbon nanotubes (CNT) are appealing additives for high-power batteries, due to their outstanding electronic conductivity, long aspect ratio necessitating low volume fraction for percolation and high flexibility. This summary describes the current state-of-the-art in Li/CFx batteries and highlights opportunities for development of high-power LI/CFx batteries via utilization of CNT. In our research, we investigated the resistivity of CFx combined with CNT and compared the CFx-CNT composites with conventional carbon additives. We investigated CFx-CNT electrodes without metallic current collectors and compared their electrochemical performance with conventional CFx electrodes using metallic current collectors. Furthermore, we fabricated multilayered CNT-CFx-CNT electrodes (sandwich-structure electrodes) and studied the influence of structure on performance of the electrode. By generating several electrode architectures using CFx-CNT combinations and investigating the impact of CNT on the electrochemical performance, we demonstrated the opportunities for utilization of CNT in CFx electrode and the promising implementation of CFx electrode in next-generation high-power batteries.
9:00 AM - LL3.08
Activated Carbon Derived from Agricultural Waste Streams for Energy Applications
Lucas Servera 1 Paul Raymond Armstrong 2 Kofi Wi Adu 2 3 Angela Lueking 1 3
1Pennsylvania State University Altoona United States2Penn State - Altoona College Altoona United States3Pennsylvania State University University Park United StatesShow Abstract
The unique structural architecture of carbon-based nanoporous structures such as activated carbon (AC) has made activated carbon one of the most viable materials to address current environmental challenges. The highly developed porosity, large surface area, tunable surface chemistry, and high degree of surface reactivity make AC the most widely used adsorbent for the removal of wide variety of organic and inorganic pollutants dissolved in aqueous media or from gaseous environments, as well as the use as electrodes in energy related applications. Traditional feedstocks for AC production include, primarily, mineral carbons, and lignocellulosics from biomass and wood. However, any cheap material, with a high carbon content and low mineral content, can be used as a precursor for the production of AC. Agricultural wastes are proving to be promising precursors for the production of ACs mainly due to their availability, low cost and zero carbon foot print. We present preliminary investigation on utilized mechanical ball milling followed by chemical activation technique to convert agricultural waste (cocoa and coconut husks, palm midribs and calabash) into ultra-high surface area activated carbon suitable for myriads of environmental and energy related applications. Our preliminary investigation indicates about 70% increase in BET surface area with ball milling to as high as ~ 3000 m2/g, and shows potential application as electrode material in supercapacitors.
9:00 AM - LL3.10
Influence of Graphene-Chitosan Nanoplateles in the Direct Electron Transfer Process of Enzymes
Tiago Pedroso Almeida 1 2 Frank Hollmann 2 Celina Massumi Miyazaki 3 Antonio Riul 1
1Unicamp Campinas Brazil2TU Delft Delft Netherlands3UFSCar Sorocaba BrazilShow Abstract
Multilayer films of Graphene-Chitosan nanoplatelets with glucose oxidase were assembled using the layer-by-layer (LbL) technique. The aim here is a better comprehension of how the presence of Graphene-Chitosan (G-Chitosan) nanosheets present in the LbL nanostructured multilayers influences the direct electron transfer process between enzyme and electrode. The LbL assembly was chosen due to its simplicity and versatility to produce thin films with controllable thickness and morphology, taking the advantage of nanoscale engineering to create tailored architectures that can hold the enzyme inside the multilayers formed, with fine control in the film composition and structure. The G-Chitosan choice was based on the possible biological compatibility and possibility to support a direct electron transfer (DET) mechanism between active center inside the enzyme and the electrode. Here, UV-vis was used to investigate the film formation and also the structure of the enzyme immobilized, which was also characterized by potentiometric measurements to check the DET process. Our results indicated good adherence and linear growth of the (G-Chitosan/Gox) LbL films, and also a DET dependence on the film structure. In summary, we believe that the LbL multilayer assembly facilitates the DET as some nanoplatelets are becoming closer to the active center of the enzymes.
9:00 AM - LL3.11
Tungsten Selenide as a High Capacity Anode for Sodium Ion Batteries
Keith Share 1 John Lewis 2 1 Landon Oakes 2 Adam Paul Cohn 2 Cary Pint 2
1Vanderbilt Univ Nashville United States2Trinity University San Antonio United StatesShow Abstract
WSe2shy; is used for the first time as a sodium ion battery anode and shows a high capacity of 253 mAh/g at a rate of 10 mA/g during the first sodium extraction. This is comparable to or higher than other commercially available transition metal dichalcogenides (TMDs). WSe2 is compared to WS2 and demonstrates a higher specific performance, better rate capability, and less capacity fade. WSe2 also shows a small overpotential of 0.25 V between the anodic and cathodic peaks which is promising for practical applications. Ex situ Raman spectroscopy, X-ray diffraction, and energy dispersive x-ray spectroscopy in the transmission electron microscope show the formation of a crystalline product with domains containing either selenium or tungsten, suggesting a conversion reaction mechanism that differs from MoS2. This work demonstrates that WSe2 is a promising material for use as an electrode in sodium ion batteries and we identify further routes, such as controlled nanostructuring, as a means to further improve the measured performance and cyclability.
9:00 AM - LL3.12
Synthesis of a Hollow TiO2 as an Anode for Lithium-Ion Batteries
Xingkang Huang 1 Junhong Chen 1
1Univ of Wisconsin-Milwaukee Milwaukee United StatesShow Abstract
A hollow TiO2 was synthesized through hydrolysis of titanium tetraisopropoxide in order to facilitate lithium ion insertion into and extraction from the TiO2 bulk. The pore size hollow TiO2 is ca. 40-100 nm with controllable wall thickness, for example, from 9 to 23 nn. The as-obtained hollow TiO2 with 13 nm wall thickness delivered an initial capacity of 255.9 mAh g-1 with an initial Coulombic efficiency of 72.8% at a current density of 10 mAh g-1. After two cycle activation, the hollow TiO2 anode was cycled at a current density of 200 mA g-1, exhibiting a capacity of 170.9 mAh g-1 at the 3rd cycle and a slightly increased capacity of ca. 176 mAh g-1 in the subsequent cycles due to the further activation of TiO2. The porous TiO2 shows excellent cyclic performance; after 200 cycles, the capacity remains at 161 mAh g-1, 91.5% of the highest capacity at 200 mA g-1. The hollow TiO2 also exhibits very good rate capability. The capacities are 254, 221, 207, 187, 173, 160, 136, and 114 mAh g-1 for the current densities of 10, 20, 40, 100, 200, 400, 1,000, and 2,000 mA g-1, respectively. The capacity of 114 mAh g-1 obtained at 2,000 mA g-1 corresponds to 44.9% and 51.6 % of those obtained at 10 and 20 mA g-1, respectively, indicating an excellent rate capability. Considering the excellent cyclic performance of the hollow TiO2, long-term cycling was performed at 400 mAh g-1 for 1,500 cycles, delivering 167 mAh g-1 while retaining 83% of the reversible capacity. In conclusion, the as-prepared hollow TiO2 possesses particle sizes of ca. 100 nm and thin wall thickness, which facilitates lithium ion insertion and extraction to allow the hollow TiO2 to deliver high capacities, excellent rate capability, and distinguished cyclic performance; therefore, the TiO2 anode is very promising for practical applications
9:00 AM - LL3.13
Decorating Fe3O4 Colloidal Nanoparticles on Graphene for High-Performance Lithium-Ion Batteries Application
Zhang Ning 1 Jia Li 1 Dickon Ng 1
1Chinese Univ of Hong Kong Hong Kong ChinaShow Abstract
In order to enhance the sustainable development of our economy and society, efforts have been made to explore new compositions or to design novel nanostructures for energy storage materials. Rechargeable lithium-ion batteries (LIBs) is one of the promising candidates. Among the available electrode materials for the Li-ion batteries, magnetite (Fe3O4) is regarded as an appealing material due to its high theoretical capacity, natural abundance as well as environmental friendly. Herein, we report a green and facile one-step method to decorate the graphene foam with uniform mono-dispersed Fe3O4 colloidal nanoparticles at room temperature. The as-synthesized hierarchical Fe3O4/graphene anode material exhibited a large reversible specific capacity (~950 mA h g-1 at 100 mA g-1), excellent cyclic stability (nearly unchanged after 200 cycles), good rate capacity and high Coulombic efficiency. This excellent electrochemical performance of Fe3O4/graphene hierarchical structures should have a great potential to be used as an active electrode for lithium-ion batteries. Moreover, such safe, cost-effective and straightforward fabrication process provides a new methodology to design and synthesize high performance anode materials for smart electrochemical energy storage systems.
9:00 AM - LL3.14
Synthesis and Crystal Structure Control of Birnessite-Type MnO2 by Solution Plasma Process and Their Characterizations
Hyemin Kim 1 Anyarat Watthanaphanit 1 2 Nagahiro Saito 1 2 3
1Graduate School of Engineering, Nagoya University Nagoya Japan2Institution of Innovation for Future Society, Nagoya University Nagoya Japan3Green Mobility Collaborative Research Center, Nagoya University Nagoya JapanShow Abstract
Manganese oxides are one of the most promising transition metal oxide materials for pseudo-capacitor, battery, catalysts, biosensor, magnetic materials and ion-exchanger because of their excellent electrochemical properties. Among them, nanostructured manganese dioxide (MnO2) have attracted great attention due to the high theoretical capacities, abundance, environmentally friendliness, low cost, and good electrochemical properties. MnO2 exists in several polymorphic forms such as α-, β-, γ-, δ-, and lambda;-types. Among them, great attention has been paid to δ-MnO2—a layered birnessite-type—due to its large capacitance and high ionic conductivity. Owing to significant relationship among the crystal structure; specific surface area; and specific capacitance, a variety of synthesis methods have been applied to obtain optimal structures of MnO2. However, multi-step process, time-energy consuming and expensive additional reagents still seem to be obstacles for the commercialization of the nanostructured manganese oxide. In this study, birnessite-type MnO2 was synthesized from potassium permanganate (KMnO4) aqueous solution by adding simple-inexpensive sugar D-glucose in the solution before generating glow discharge plasma, at room temperature and atmospheric pressure. To control structural properties of the synthesized MnO2, the frequency conditions were varied as 15, 25, 35 and 45 kHz. As the frequency was increased, processing time was shorten from 15 to 5 min. Differentiation of the synthesized MnO2 were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) method, and Raman spectroscopy. Crystallinity and specific surface area of the synthesized MnO2 were successfully controlled by the discharge conditions. These findings suggest that solution plasma process is an effective method to control the optimal structure of nanostructured MnO2.
9:00 AM - LL3.15
Cobalt Phthalocyanine Analogues as Soluble Catalysts that Improve the Charging Performance of Li-O2 Batteries
Shoichi Matsuda 1 Shigeki Mori 2 Yoshimi Kubo 3 Kohei Uosaki 3 Kazuhito Hashimoto 1 Shuji Nakanishi 1
1The University of Tokyo Tokyo Japan2Ehime University Ehime Japan3National Institute for Materials Science Ibaraki JapanShow Abstract
A non-aqueous aprotic Li-air battery is a promising device for future energy management systems, because Li-air batteries can potentially exhibit much higher energy density than today&’s Li ion batteries. Development of electrocatalysts for the oxygen evolution reaction (OER) in aprotic Li ion electrolytes accompanied with Li2O2 decomposition is a critical challenge to be addressed toward the realization of rechargeable Li-air batteries with high round trip efficiency. One approach to overcome this inherent problem with electrocatalysts is to use a soluble catalyst that can repeatedly adsorb on the growing or dissolving Li2O2 front. However, the solubility of the catalyst used so far was less than several millimoles per liter, which would prevent further improvement of the charging performance.
In this study, we demonstrates that the tert-butyl cobalt phthalocyanine (tb-CoPc) and analogues serves as a soluble catalyst on the positive electrode for rechargeable Li-O2 batteries. The cell containing tb-CoPc displayed superior charging performance, exhibiting the potential of about 3.3 V at the initial stage of the charging process. Importantly, the superior discharge/charge processes accompanied with reversible formation and decomposition of Li2O2 indicated that tb-CoPc function as OER catalyst without changing the reaction scheme.
The effect of tb-CoPc addition on the discharge/charge characteristics was investigated using a coin type cell. Although both cells showed a stable discharge potential at around 2.7 V, there is a clear difference between the charging profiles. For the cell without tb-CoPc, the charging potential was around 4.0 V and then finally reached ca. 4.3 V. In contrast, the cell with 10 mM tb-CoPc exhibited better charging performance. To confirm the effect of the high solubility of tb-CoPc, the effect of CoPc addition, which has lower solubility than tb-CoPc due to the lack of tert-butyl-groups, was investigated. The solubility of CoPc in the representative Li-ion electrolyte that was used (i.e., 1 M Li trifluoromethanesulfonate dissolved in triethylene glycol dimethyl ether (TEGDME)) was not more than 1 mM. Notably, the redox potential of tb-CoPc is more negative than that of CoPc, which is also advantageous for the charging process. However, the charging performance was not so improved when the concentration of tb-CoPc is 1 mM, indicating that the improved charging performance in the presence of 10 mM tb-CoPc is mainly due to the higher solubility of tb-CoPc compared with CoPc.
In conclusions, we have demonstrated that tb-CoPc functions as a soluble catalyst on the positive electrode for rechargeable Li-O2 batteries. The results obtained here reveal the importance of an appropriate design for the soluble catalyst in rechargeable Li-air batteries to achieve high round-trip energy efficiency.
9:00 AM - LL3.16
GITT Diffusion Coefficient of Single-Phased Lithium Iron Phosphate Thin Films Grown by Pulsed Laser Deposition
Alexander M Moeller 1 Patrick Schichtel 1 Joachim Sann 1 Juergen Janek 1
1Univ of Giessen Giessen GermanyShow Abstract
Lithium iron phosphate (LFP) has been proposed in 1997 by Padhi et al.  as a cathode material for lithium ion batteries. It is a cheap, environmentally friendly and prone to build batteries with very long lifetimes, since the electrochemical potential of LFP ist well inside the stability window of most liquid electrolytes. The material has since been subject to a lot of research and is widely commercially available, however, the mechanism of lithium insertion and depletion is still under discussion [2-4]. Batteries consist of many parts and usually contain a multitude of active materials and additives. In order to avoid overlapping effects or side reactions, detailed studies of a material require a reduced complexity. Thin films are one approach in reducing the complexity of systems. Due to the short diffusion paths, thin films usually do not require conducting additives. Furthermore, a smooth surface is a well defined area in comparison to rough or even porous particle samples.
In this study thin films of carbon-free LiFePO4 with a thickness of about 200 nm have been prepared on silicon substrates by pulsed laser deposition. From these thin films we build electrochemical cells with 0.1 M LiBOB in a 1:1 mixture of EC/DMC electrolyte and a lithium anode.
The cells were used to perform Galvanostatic intermittend tittration technique (GITT) measurements. From the data obtained by this technique it is possible to calculated the diffusion coefficients of single-phased systems from the change of the equilibrium voltage with the lithium concentrations. In the case of the two phase system LFP this should in principle not work, because the equilibrium voltage for different concentrations of lithium should be constant.
However, the GITT measurements on our samples showed that the equilibrium voltages indeed depends on the lithium concentrations. This implies a single-phase material at the surface of the thin film. Therefore, the analysis with the GITT equation was possible and the diffusion coefficients were determined to be between 3#8901;10-12 cm2s-1 to 8#8901;10-12 cm2s-1. We present a model to explan our findings.
 Padhi, A. K.; Nanjundaswamy, K. & Goodenough, J., Journal of The Electrochemical Society, 1997, 144, 1188
 Srinivasan, V. & Newman, J., Journal of The Electrochemical Society, 2004, 151, A1517
 Malik, R.; Abdellahi, A. & Ceder, G., Journal of The Electrochemical Society, 2013, 160, A3179-A3197
 Delmas, C.; Maccario, M.; Croguennec, L.; Le Cras, F. & Weill, F., Nat Mater, 2008, 7, 665
9:00 AM - LL3.17
Etched Silicon Anode for High Performance Lithium-Ion Capacitor
Martin Halim 2 1 Chairul Hudaya 3 A-Young Kim 1 Un Seok Kim 1 Joo Man Woo 1 Joong Kee Lee 2 1
1Korea Institute of Science and Technology Seoul Korea (the Republic of)2Korea University of Science and Technology Daejeon Korea (the Republic of)3University of Indonesia Depok IndonesiaShow Abstract
Li-ion capacitors (LICs) recently gained much attention because they combine both high power density of supercapacitors and high energy density of lithium-ion batteries. In these work, we propose a high performance LIC based on etched silicon anode material that was synthesized by metal-assisted chemical etching technique. The physical properties of etched silicon are analyized by SEM, BET, XRD, XPS, and TEM. Prior to full cell assembly, the etched silicon is lithiated to 0.01 V vs Li/Li+ and then is paired with high surface area activated carbon as the cathode, polypropylene as separator and 1.3 M LiPF6 in ethylene carbonate and dimethyl carbonate (3:7 volume ratio) as electrolyte. The full cell was then subjected to several electrochemical analysis including cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic cycle test at different current density. The results show that the LIC based on the etched silicon is able to remarkably retain nearly 90% of its initial capacitance even after 50,000 cycles at high current density. The improved electrochemical performance is attributed to the structural design of silicon anode, which provides a porous material, thereby increasing the specific surface area of anode, promoting an easy electrolyte access and accelarating the Li-ions diffusion.
9:00 AM - LL3.18
Sn Negative Electrode Consists of Amorphous Structures for Lithium Ion and Sodium Ion Secondary Batteries
Naoki Okamoto 1 Koki Morita 1 Takatomo Fujiyama 1 Takeyasu Saito 1 Kazuo Kondo 1
1Osaka Prefecture Univ Sakai JapanShow Abstract
Tin(Sn) and its alloys have been attracting attentions as a negative electrode material for lithium-ion and sodium-ion secondary batteries with high theoretical capacity (Li22Sn5, ca. 990 mAh#65381;gminus;1) and high electromotiveforce. There still remains the issue as regards the discharge capacity decrease with increasing the number of cycles. In order to improve cycle performance, there are many studies such as using Sn-Ni alloy, macroporous patterns and enhancing adhesiveness of active materials. However, most of these studies are using Sn based alloy as negative electrode materials and it suffer from the disadvantage of lowering of discharge capacity. In this study, a deposition process for making Sn film which consists of amorphous structure for negative electrode of lithium ion secondary batteries utilizing electordeposition from aqueous bath was developed. The effect of additives on the surface morphology and microstructure of Sn film was investigated. Furthermore, we evaluated the effect of amorphous structure in the Sn film on cycle performance of the Sn negative electrode. The Sn film was formed by electrodeposition using aqueous bath at low temperature. Cu foil with a thickness of 35 mu;m was used for the substrates We used 5 types of Sn deposition bath. Tin sulfate (SnSO4) and tin chloride (SnCl2) were used as metal resource reagents. Phosphinic acid (H2PO2), boric acid (H3BO3) and potassium sulfate (K2SO4) were used as additives. In addition, conventional Sn deposition bath, which consists of 30 g Lminus;1 (0.14 M) tin sulfate (SnSO4), 96 g Lminus;1 sulfuric acid (H2SO4) and 100 ppm polyethylene glycol (PEG, Mw: 4000), was used for comparison. Both amorphous and crystalline structure was observed in the deposited Sn film. In contrast to conventional Sn electrodeposited film, this unique Sn film has a good cycle characteristic (>50 cycles) and discharge capacity (> 400 mAh#65381;g-1). Furthermore, in the case of using the bath which includes phosphinic acid (H2PO2) in composition discharge capacity after first cycle approached over 700 mAh g-1 and that of after fifties cycle was over 400 mAh g-1. Amorphous structure in the Sn film showed a microscopic effect on the volume change by lithiation and delithiation.
9:00 AM - LL3.19
Comparative Study of Activation Methods to Form Thermosetting Resin-Based Active Carbon Particles for Electric Double Layer Capacitor
Takeyasu Saito 1 Takafumi Nakazawa 1 Yuichi Tsujimoto 1 Koichi Nishimura 1 Naoki Okamoto 1 Kazuo Kondo 1 Isamu Ide 2 Masanobu Nishikawa 2 Yoshikazu Onishi 2
1Osaka Prefecture Univ Sakai Japan2LIGNYTE. CO.,LTD Sakai JapanShow Abstract
Electric double layer capacitor (EDLC) has been attracted much attention as one of the most promising high power and durable energy storage devices. However, low energy density is the major drawback, therefore, the optimization of active carbon specific surface area, mesoscale pore volume and electrostatic capacity should be necessary.
In this study, we prepared thermosetting resin (phenol resin and furfural resin, 10 mm in diameter)-based active carbon particles in N2 atmosphere in three hour (temperature rising rate: 10C /min) at 6000C. Then we treated those samples by three kinds of methods, KOH activation (KOH: samples = 4: 1 in weight), CO2 activation or a combination of KOH and CO2 activation. All activation methods were carried out for 30 minutes at 8000C (temperature rising rate: 100C /min). Specific surface area/pore size distribution measurement was carried out using N2 adsorption. We prepared two coin-shaped carbon electrodes (as working and counter electrodes, 14 mm in diameter), and investigated the electrostatic characteristics of the capacitors in 6M KOH to elucidate the relationship between physical and electrochemical properties.
We obtained phenol resin based active carbon having large specific surface area, 1253 m2/g and 1240 m2/g, by KOH and KOH+CO2 activation methods, respectively, however, we could not only by CO2 activation method (515 m2/g). The volumic mesopore ratio of KOH, KOH+CO2, and CO2 activation methods were 8.4, 12.8, and 8.8, respectively. Using CO2 activation did not result in specific surface area development, however, CO2 activation after KOH treatment increased mesopore ratio with keeping large specific surface area. In all activation methods, electrostatic capacity improved with increasing specific surface area.
Specific surface area of phenol resin derived carbon particles was almost the same by both KOH and KOH+CO2 activation methods, however, electrostatic capacity after CO2 activation was improved from 109 F/g to 163 F/g at 20mA/cm2. The same trend was also observed with the cases of furfural resin derived carbon particles. The best electrostatic capacity of activated carbon particles from phenol resin and furfural resin were 163 F/g and 119 F/g at 20mA/cm2, respectively, in this study
9:00 AM - LL3.20
Lithium Iron Phosphate Batteries Using Three-Dimensional Metal Foam as Current Collector
Kyung Yup Song 1 Gui Fu Yang 1 Gil Su Jang 1 Seung Ki Joo 1
1Seoul National University Seoul Korea (the Republic of)Show Abstract
We fabricated three-dimensional metal foam for current collector of positive electrode and demonstrated a high electrochemical performance of lithium iron phosphate batteries. Electrode was made by filling LiFePO4 into 600 µm pore size and 1000 µm thick Al metal foam. As a result of applying 5, 6, 7, 8, 9, 10 mA to 10 cycled single, double and triple stacked electrode, 5 mA of triple and double stacked electrode showed highest capacity which was 130 mAh/g. and single electrode showed low capacity, approximately 113 mAh/g. C-rate gets lower because double and triple stacked electrode have much more active material mass. But by measuring 60 cycles to 10 mA, the coulombic efficiency of single, double and triple layer cell was 50, 35, and 30 %, respectively. Triple layer cell showed lowest capacity which was 40 mAh/g. When it cycles while increasing current, Lithium diffusion distance gets longer as electrode becomes thicker. So lithium cannot diffuse from inner part to surface and get stacked inside.
9:00 AM - LL3.21
Au Embedded ZnO /NiO Hybrid with Excellent Electrochemical Performance as Advanced Electrode Materials for Supercapacitor
Xin Zheng 1 Xiaoqin Yan 1 Yihui Sun 1 Yue Zhang 1
1School of Materials Science and Engineering, University of Science and Technology Beijing Beijing ChinaShow Abstract
Here we design a nanostructure by embedding Au nanoparticles into ZnO/NiO core-shell composites as supercapacitors electrodes materials. This optimized hybrid electrodes exhibited an excellent electrochemical performance including a long-term cycling stability and a maximum specific areal capacitance of 4.1 F/cm2 at a current density of 5 mA/cm2, which is much higher than that of ZnO/NiO hierarchical materials (0.5 F/cm2). Such an enhanced property is attributed to the increased electro-electrolyte interfaces, short electron diffusion pathways and good electrical conductivity. Apart from this, electrons can be temporarily trapped and accumulated at the Fermi level (EF') due to the localized schottky barrier at Au/NiO interface in charge process until fill the gap between ZnO and NiO, so that additional electrons can be released during discharge. These results demonstrate that suitable interface engineering may open up new opportunities in the development of high-performance supercapacitors.
This work was supported by the National Major Research Program of China (2013CB932602), the Major Project of International Cooperation and Exchanges (2012DFA50990), the Program of Introducing Talents of Discipline to Universities, NSFC (51232001, 51172022, 51372023, 51372020), the Research Fund of Co-construction Program from Beijing Municipal Commission of Education, the Fundamental Research Funds for the Central Universities, the Program for Changjiang Scholars and Innovative Research Team in University.
 Ellis, B.; Knauth, L., Three-Dimensional Self-Supported Metal Oxides for Advanced Energy Storage. Adv. Mater. 2014, 26, 3368-3397.
 Zheng, X.; Sun, Y.; Yan, X.; Chen, X.; Bai, Z.; Zhang, Y., Tunable Channel Width of A UV-Gate field Effect Transistor Based on ZnO Micro-Nano Wire. RSC Adv. 2014, 4, 18378-18381.
 Lu, X.; Zhai, T.; Zhang, X.; Shen, Y.; Yuan, L.; Hu, B.; Gong, L.; Chen, J.; Wang, Z., WO3-x@Au@MnO2 Core-Shell Nanowires on Carbon Fabric for High-Performance Flexible Supercapacitors. Adv. Mater. 2012, 24, 938-944.
 Liao, Q.; Mohr, M.; Zhang, X.; Zhang, Z.; Zhang, Y.; Fecht, H., Carbon Fiber-ZnO Nanowire Hybrid Structures for Flexible and Adaptable Strain Sensors. Nanoscale, 2013, 5, 12350-12355.
9:00 AM - LL3.22
Influence of Oxygen Plasma Treatment on Electrolyte Wettability and Electrochemical Performance of Polyethylene Separator for Lithium Ion Battery
So Yeon Jin 1 Jayoung Cheon 1 HunMin Lee 1 Won Ho Park 1
1Chungnam National Univ Daejeon Korea (the Republic of)Show Abstract
Lithium-ion batteries (LIBs) have been extensively developed in the recent years, owing to its high energy density and excellent cycle life. As an important representative of the class, LIBs have been widely used in portable electronics such as electronic equipments, mobile products, and communication devices.
Separator plays an important part in lithium-ion battery. Polyolefin separators such as polypropylene (PP) and polyethylene (PE) are one of the most widely used separators of lithium-ion battery, because polyolefin separator have good mechanical properties, chemical stability and effectively prevent thermal runaway caused by electrical short-circuits or overcharging. However, they do not readily adsorb the electrolyte solvent due to their hydrophobic surface with low surface energy, and have poor ability in retaining the electrolyte solutions and therefore often require a modification of their surface properties before use.
To overcome these disadvantages of polyolefin separators, various methods including the modification of polyolefin separator, preparation composite separator, and development of new materials used for separator, plasma treatment and physical/chemical vapor deposition have been developed to improve hydrophilicity of the polyolefin separator. Surface modification by plasma is the green process to modify the surface of the polymeric materials.
In this study, the surface of PE separator was modified by oxygen plasma treatment for high-performance lithium-ion battery. The changes of surface morphology were observed by using Field Emission Scanning Electron Microscopy (FE-SEM). The chemical composition of the surface was analyzed using X-ray photoelectron spectroscopy (XPS) and Attenuated total reflection infrared spectroscopy (ATR-IR). Oxygen plasma treatment improved a variety of properties of PE separator such as the electrolyte retention, the electrolyte wettability, and high ionic conductivity. In addition, the electrochemical characteristics of plasma-modified PE separator showed the improved charge-discharge test, and the cells showed stable cycling performance. The results indicated that the plasma-modified PE separator qualifies as a potential application in lithium-ion battery.
9:00 AM - LL3.23
Cucurbituril-Oxovanadium(IV) Complex Intercalation into Vanadium Pentoxide for Lithium Battery Cathode Materials.
Francisco de Araujo Silva 1 Silvania Marilene de Lima 1 Fritz Huguenin 1 Gregoire Jean-Francois Demets 1
1Universidade de Satilde;o Paulo Ribeirao Preto BrazilShow Abstract
Lithium batteries are important devices and several different anode and cathode combinations have been studied to enhance storage capacity, cyclability, and other characteristics.
Vanadium pentoxide (V2O5.nH2O) is a very useful material for lithium batteries cathodes, displaying good conductivity, capacity storage, easy to synthesize and it has a lamellar structure allowing ions intercalation. Due to different types of Li+ intercalation sites, it is common to observe structural modifications during charge/discharge cycles assigned to structural stress which leads to irreversible Li+ trapping inside this matrix, decreasing its storage capacity.
Cucurbit[n]urils (CB[n]) are a family of hollow toroidal macrocycles obtained by condensation of n glycoluril units and formaldehyde. Our group have intercalated CB into the interlamellar gap of lamellar double hydroxides (LDH) and we could show that the macrocycle works as a pillar, supporting and maintaining the lamellar structure.
We have intercalated a series of macrocycles into V2O5.nH2O such as CB, CB and HCB to act in a same way avoiding rearrangements, however, the carbonyl oxygens of both portals seem to trap Li+ ions by themselves. To solve this problem, we have pillarized the structure with a CB vanadyl complex (CBVO), where a VO2+ ion avoids Li+ coordination.
The presence of CBVO into V2O5.nH2O stabilizes the oxide structure avoiding rearrangements and offers alternative pathways for lithium ions diffusion.
 F. de A. Silva, F. Huguenin, S. M. de Lima and G. J. F. Demets, Inorg. Chem. Front. 2014, 1, 495.
 G. J. F. Demets, Quim. Nova, 2007, 30, 1313-1322.
 L. F. S. da Silva, G. J. F. Demets, C. Taviot-Guého, F. Leroux and J. B. Valim, Chem. Mater., 2011,23, 1350-1352.
9:00 AM - LL3.24
Synthesis of Low-Cost, High-Performance Electrode Materials for Na-Ion Batteries Using Ultrasonic Spray Pyrolysis
Mayuri Razdan 1
1Purdue University West Lafayette United StatesShow Abstract
Medium-to-large scale energy storage systems require battery technologies comprising both abundant, low-cost materials and inexpensive fabrication methods. Na-ion batteries (NIB), often considered a potential successor of the lithium ion battery (LIB) technology for medium-to-large scale systems, can approach the energy and power densities of current state-of-the-art battery technologies while significantly reducing material and fabrication cost. A variety of possible NIB chemistries have been successfully demonstrated, in most cases, however, material design and fabrication have followed the cost-intensive approaches of the LIB technology. Here, we report on the development of NIB electrodes, taking into consideration not only performance criteria, but also material and manufacturing cost. Both anode (carbon composite) and cathode (layered metal oxide) were fabricated by ultrasonic spray pyrolysis, a solution-based, easy-to-scale process. Structure and composition were studied using tip-enhanced Raman spectroscopy, scanning electron microscopy, and X-ray diffraction. Electrochemical performance was evaluated in half-cell (vs. Na) and full-cell configuration by analyzing cell impedances, charge-discharge voltage profiles, rate performance, and cycle life.
9:00 AM - LL3.25
Zn2+-Ion Intercalation: A Pathway to Understand Multivalent Ion Intercalation Phenomena
Premkumar Senguttuvan 1 Sang-Don Han 1 Anthony Burrell 1 Christopher Johnson 1
1Argonne National Laboratory Lemont United StatesShow Abstract
New high-energy density battery systems are needed to elevate energy densities beyond that of Li-ion batteries, particularly if we are to meet increasing energy storage demands worldwide. Certainly the chemistry paths beyond lithium-ion systems are large and portend immense opportunities. One key approach in targeting new chemistries/systems is to employ lessons learned from lithium-ion battery technology. Indeed the evolution of lithium batteries has originated from redox intercalation chemistry which is based on inserting lithium ions into empty crystallographic sites of a host material and exchanging equivalent charge with via transition metal redox couples . The same concept could also be extended to insert bi- or tri-valent ions in the place of monovalent ions inside the host material and thereby increasing the number of electrons exchanged in the host material . While the multivalent concept has merit and is strongly pursued, unless higher voltage oxide-based cathodes can be employed, then development of high-energy multivalent systems is hindered. Essentially oxide host materials are severely plagued by slow solid-state diffusion of multivalent ions inside the lattice due to stronger interaction of multivalent ions compared to monovalents. Additionally the integration of such cathodes into the full battery is hampered due to incompatibility with electrolytes. In comparison with other multivalent ion species (e.g. Mg2+, Ca2+, Al3+ and Y3+), the pursuit of non-aqueous Zn2+-ion intercalation chemistry has been limited, primarily by its unattractive low oxidation potential. However, thanks to some recent positive improvements in non-aqueous Zn2+-ion electrolytes, our group has embarked on systematic studies related to Zn-ion intercalation properties of various oxide host materials and this presentation will cover the latest developments. A number of important physico-chemical parameters will be explained and reported, such as redox potentials, number of electrons exchanged and structural transformations upon intercalation/de-intercalation phenomena. Design rules and comparisons of Zn2+-ion intercalation properties to that of Mg2+-ion will be discussed as well.
1) M. S. Whittingham, Chem. Rev., 2004, 104, 4271.
2) J. Muldoon, C. B. Bucur, T. Gregory, Chem. Rev. 2014, 114, 11683.
3) E. Gocke, W. Schramm, P. Dolscheid, R. Schollhorn, J Solid State Chem., 1987, 70, 71.
This work was supported as part of the Joint Center for Energy Storage
Research, an Energy Innovation Hub funded by the U. S. Department of Energy, Office of Science, Basic Energy Sciences. Work done at Argonne and use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Argonne National Laboratory, were supported by the U.S. Department of Energy under Contract No. DE-AC02-06CH11357
9:00 AM - LL3.26
Structural and Electrochemical Investigations on Mn Rich Layered Composite Cathode Materials for High Energy Density Li-Ion Batteries
Jifi Shojan 1 Loraine Torres 1 Venkateswara Rao Chitturi 1 Rajesh Katiyar 1 Shojan Pavunny 1 Ram S. Katiyar 1
1University of Puerto Rico San Juan United StatesShow Abstract
Among the entire battery family, lead acid (LA) batteries, nickel metal hydride (NiMH) batteries, and lithium ion batteries (LIBs), have great potentials for terrestrial and non-terrestrial electrochemical energy storage applications. Among all the above mentioned energy storage devices, Li ion batteries have received intensive research and development focus because of their high energy density, long cycle life, and superior environmental friendliness. Performance of Li-ion battery has to be improved for satisfying the requirements of advanced technologies like plug in hybrid electric vehicles (PHEV) and hybrid electric vehicles (HEV), in which high energy storage devices are essential. Li2MnO3 based composite cathode materials are capable of providing better electrochemical performance than layered, spinel or olivine cathode materials as their structure-stabilizing components provide better stability. Also when they are charged above 4.6 V, a very high value of specific capacity is obtained. These characteristics are enormously attractive for high energy Li ion batteries. But the irreversible capacity loss is a retracting factor for these types of cathode materials. We synthesized Li2MnO3 based composite cathode material with layered LiNi0.66Co0.17Mn0.17O2 and LiNi0.5Mn0.5O2. Our main aim is to reduce the use of cobalt as much as possible and make the cathode material safe and economic. Surface characterization proved the phase formation, crystalinity, size, and presence of constituent particles in the as prepared composite cathode material. Electrochemical characterization shows improved cathode performance in terms of rate capability test and cyclability tests. Cyclic voltametry studies and electrochemical impedance spectroscopy studies confirmed the potential applicability of the composite cathode material for Li ion battery technology. To understand the effect of Co concentration in the cathode material we will present a comparative study on the performances of composite cathode material with and without LiNi0.5Mn0.5O2.
9:00 AM - LL3.27
System Cost and Performance Analysis for Grid Storage: Lithium-Polysulfide Flow Battery
Seungbum Ha 1 2 Kevin Gallagher 1 2
1Argonne National Laboratory Lemont United States2Joint Center for Energy Storage Research Lemont United StatesShow Abstract
A demand for grid energy storage systems is increasing for extensive deployment of renewable energy such as solar and wind systems. Scalable energy storage with low cost will be a key to meet these challenges.
Non-aqueous Lithium-polysulfide(Li-PS) flow batteries are of particular interest due to their scalability, high potential chemistries, and potentially low cost for grid storage applications.
While top-down models for Li-PS flow battery have been developed, they have not examined in detail the electrochemical performance and materials cost using bottom-up approach.
Here we present a comprehensive assessment of system cost analysis for nonaqueous Li-PS flow battery and the model examines the correlation between performance and cost as considering the physical property limitations of the system components and manufacturing.
Additionally, the comparison with enclosed Li-ion system allows a deeper understanding of the design phase space for the requirements of an application
9:00 AM - LL3.28
Designs and Operation of Non-Flowing Zinc Bromine Battery with Low-Cost Materials
Shaurjo Biswas 1 2 Aoi Senju 1 2 Daniel Steingart 1 2
1Princeton University Princeton United States2Princeton University Princeton United StatesShow Abstract
Although Zinc Bromine (Zn-Br2) secondary batteries have been studied for decades as a low cost, fully rechargeable, high density energy storage system, the large scale and widespread commercial implementation of this technology has not yet been realized due to two key limitations: i) Self-Discharge: Elemental bromine, Br2 (l) generated during the charging cycle tends to convect and diffuse through the aqueous zinc bromide electrolyte to the Zn counter electrode, thus self-discharging the cell. ii) Zinc Dendrites: Repeated electroplating and dissolution of zinc during charging/discharging of the cell leads to the formation of dendrites, which can grow to eventually form a conductive bridge from the anode to the cathode and short-circuit the cell.  Zn-Br2 flow-cells alleviate these limitations by adding bromine complexing agents and by flowing electrolyte to reduce Zn dendrite formation, respectively, albeit at the cost of cell resistance, battery efficiency, size, and capital costs. 
In this work, we demonstrate a simple, low-cost, non-flowing Zn-Br2 cell design, possibly without the use of complexing agents. We discuss strategies for local containment of Br2 (l) by leveraging its unique physical chemistry as well as using innovative electrode design.
The prevention of undesired Zn dendrite formation issue is addressed by using a nano-structured Zn electrode which has a more uniform growth front compared to dendritic Zn. The formation of nano-structured Zn is described elsewhere . Our model test cell consists of 18 mL of 2M ZnBr2 aqueous electrolyte which yields specific charging capacities of 155.6 and 138.8 mAh/g of electrolyte at current densities of 1.0 and 5.0 mA/g, respectively. The discharge specific energy of over 100 Wh/kg at 5 mA/g is recorded, with a Coulombic efficiency of over 90%. This is a high capacity battery considering that the cost of all the materials going into the cell is $39.50/cell inclusive of passives. Unlike traditional Zn-Br2 systems we do not use a pump. The electrochemical characteristics of this non-flowing Zn-Br2 cell are further discussed in terms of cell resistance, specific capacity, energy and coulombic efficiencies, and cycle life. Finally, we provide a novel visible light method for examining the current distribution and bromine concentration within the cell.
 P.C. Butler et al. Handbook of Batteries,Ed. 3, Ch. 39, McGraw-Hill, Ohio (2001)
 D. Ayme-Perrot et al., J. Power Sources (2008) 175, 644
 M. Chamoun et al., NPG Asia Materials (2015) 7, e178
9:00 AM - LL3.29
Relationship between Carbon Electrode Materials and Electrolytes in Capacitive Energy Storage
Katherine Van Aken 1 Majid Beidaghi 1 Yury Gogotsi 1
1Drexel Univ Philadelphia United StatesShow Abstract
Electrochemical capacitors (ECs) use a very different charge storage mechanism than batteries, relying on the physical adsorption of ions on a high surface area material instead of chemical reactions. ECs can yield a power density of more than 10x that of batteries, however, they provide about 10x less energy density. Since the energy density of the device is proportional to the square of operating potential window, an effective way to increase energy density of the device is by increasing this voltage window. Theoretically, ionic liquid electrolytes can operate at up to 6 V, though experimentally, the value is between 3-4 V, depending on the properties of electrode materials. Though they boast a large operating potential window, ionic liquids are known to contain large and bulky ions. This can make it difficult to use an ionic liquid on a porous carbon with a range of pore sizes, even though the specific surface area of the electrode material is higher. It has also been shown that the capacitance of porous electrodes