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Sample records for mno2 aqueous rechargeable

  1. Development of MnO2 cathode inks for flexographically printed rechargeable zinc-based battery

    NASA Astrophysics Data System (ADS)

    Wang, Zuoqian; Winslow, Rich; Madan, Deepa; Wright, Paul K.; Evans, James W.; Keif, Malcolm; Rong, Xiaoying

    2014-12-01

    A novel roll-to-roll flexographic printing process for rechargeable zinc-based battery manufacturing was presented in this paper. Based on the fundamental operating mechanism of flexography, key criteria for developing functional flexographic printing inks were established, including composite ink rheology (steady-state viscosity and yield stress), ink wettability as well as ink dispersing qualities. A variety of MnO2 cathode inks were developed and analyzed comprehensively based on these criteria. A novel type of aqueous cathode ink based on PSBR polymeric binder showed excellent flexographic printability as well as promising electrochemical performance.

  2. Aqueous ultracapacitors using amorphous MnO2 and reduced graphene oxide

    NASA Astrophysics Data System (ADS)

    Mery, Adrien; Ghamouss, Fouad; Autret, Cécile; Farhat, Douaa; Tran-Van, François

    2016-02-01

    Herein, synthesis and characterization of amorphous MnO2 and application in asymmetric aqueous ultracapacitors are reported. Different amorphous manganese oxide (MnO2) materials were synthesized from the reduction of KMnO4 in different media such as ethanol (EtOH) or dimethylformamide (DMF). The electrochemical behavior of amorphous MnO2, labeled MnO2-Et and MnO2-DMF, were studied by using cyclic voltammetry, impedance spectroscopy, and galvanostatic cycling in aqueous electrolyte. XRD, BET, TEM, and SEM characterizations highlighted the amorphous nature and the nanostructuration of these MnO2 materials. BET measurement established that these amorphous MnO2 are mesoporous. In addition, MnO2-Et exhibits a larger specific surface area (168 m2 g-1), a narrower pore diameters distribution with lower diameters compared to MnO2-DMF. These results are in agreement with the electrochemical results. Indeed, MnO2-Et shows a higher specific capacitance and lower impedance in aqueous K2SO4 electrolyte. Furthermore, aqueous asymmetric ultracapacitors were assembled and studied using amorphous MnO2 as positive electrode and reduced graphene oxide (rGO) as negative electrode. These asymmetric systems exhibit an electrochemical stability for more than 20,000 galvanostatic cycles at current density of 1 A g-1 with an operating voltage of 2 V.

  3. A new concept for high-cycle-life LEO: Rechargeable MnO2-hydrogen

    NASA Technical Reports Server (NTRS)

    Appleby, A. J.; Dhar, H. P.; Kim, Y. J.; Murphy, O. J.

    1989-01-01

    The nickel-hydrogen secondary battery system, developed in the early 1970s, has become the system of choice for geostationary earth orbit (GEO) applications. However, for low earth orbit (LEO) satellites with long expected lifetimes the nickel positive limits performance. This requires derating of the cell to achieve very long cycle life. A new system, rechargeable MnO2-Hydrogen, which does not require derating, is described here. For LEO applications, it promises to have longer cycle life, high rate capability, a higher effective energy density, and much lower self-discharge behavior than those of the nickel-hydrogen system.

  4. MnO2-x nanosheets on stainless steel felt as a carbon- and binder-free cathode for non-aqueous lithium-oxygen batteries

    NASA Astrophysics Data System (ADS)

    Wei, Z. H.; Zhao, T. S.; Zhu, X. B.; Tan, P.

    2016-02-01

    Manganese dioxide (MnO2) has been recognized as an effective catalyst for the oxygen reduction and oxygen evolution reactions in non-aqueous lithium-oxygen batteries. However, a further improvement in battery performance with the MnO2 catalyst is limited by its low electronic conductivity and catalytic activity, which strongly depend on the morphology and composition. In this work, we develop a carbon- and binder-free MnO2-x nanosheets/stainless steel (SS) cathode via a simple and effective electrodeposition-solvothermal route. The created Mn(III) and oxygen vacancy in MnO2-x nanosheets allows an significant increase in the electronic conductivity and catalytic activity. It is experimentally shown that the use of the present nanostructure MnO2-x/SS cathode in a non-aqueous lithium-oxygen battery results in a rechargeable specific capacity of 7300 mAh g-1 at a current density of 200 mA g-1, which is 39% higher than that with the MnO2/SS cathode. In addition, the specific capacities at 400 mA g-1 and 800 mA g-1 reach 5249 mAh g-1 and 2813 mAh g-1, respectively, which are over 30% higher than that with the MnO2/SS cathode. Furthermore, the discharge/charge cycle test shows no degradation for 120 cycles. All the results show that the present nanostructure MnO2-x/SS cathode is a promising candidate for high-performance lithium-oxygen batteries.

  5. Rechargeable hybrid aqueous batteries

    NASA Astrophysics Data System (ADS)

    Yan, Jing; Wang, Jing; Liu, Hao; Bakenov, Zhumabay; Gosselink, Denise; Chen, P.

    2012-10-01

    A new aqueous rechargeable battery combining an intercalation cathode with a metal (first order electrode) anode has been developed. The concept is demonstrated using LiMn2O4 and zinc metal electrodes in an aqueous electrolyte containing two electrochemically active ions (Li+ and Zn2+). The battery operates at about 2 V and preliminarily tests show excellent cycling performance, with about 90% initial capacity retention over 1000 charge-discharge cycles. Use of cation-doped LiMn2O4 cathode further improves the cyclability of the system, which reaches 95% capacity retention after 4000 cycles. The energy density for a prototype battery, estimated at 50-80 Wh kg-1, is comparable or superior to commercial 2 V rechargeable batteries. The combined performance attributes of this new rechargeable aqueous battery indicate that it constitutes a viable alternative to commercial lead-acid system and for large scale energy storage application.

  6. Electrochemical study of aqueous asymmetric FeWO4/MnO2 supercapacitor

    NASA Astrophysics Data System (ADS)

    Goubard-Bretesché, Nicolas; Crosnier, Olivier; Buvat, Gaëtan; Favier, Frédéric; Brousse, Thierry

    2016-09-01

    The concept of an asymmetric FeWO4/MnO2 electrochemical capacitor cycled in a neutral aqueous electrolyte is presented for the first time. Commercially available cryptomelane-type MnO2 and synthesized nanocrystalline FeWO4 were used as positive and negative electrode materials, respectively. Prior to assembling the cell, the electrodes have been individually tested in a 5 M LiNO3 electrolyte solution to define both the adequate balance of active material in the supercapacitor and the proper working voltage window. Then, the full asymmetric device has been cycled between 0 and 1.4 V for over 40,000 cycles and subjected to accelerated ageing tests under floating conditions at different voltages, without any significant change on its electrochemical behavior. This remarkable stability shows the interest of developing full oxide-based asymmetric supercapacitors operating in non-toxic aqueous electrolytes that could compete with commercial carbon-based electrochemical double-layer capacitors.

  7. Co3O4 nanoparticle-modified MnO2 nanotube bifunctional oxygen cathode catalysts for rechargeable zinc-air batteries

    NASA Astrophysics Data System (ADS)

    Du, Guojun; Liu, Xiaogang; Zong, Yun; Hor, T. S. Andy; Yu, Aishui; Liu, Zhaolin

    2013-05-01

    We report the preparation of MnO2 nanotubes functionalized with Co3O4 nanoparticles and their use as bifunctional air cathode catalysts for oxygen reduction reaction and oxygen evolution reaction in rechargeable zinc-air batteries. These hybrid MnO2/Co3O4 nanomaterials exhibit enhanced catalytic reactivity toward oxygen evolution reaction under alkaline conditions compared with that in the presence of MnO2 nanotubes or Co3O4 nanoparticles alone.We report the preparation of MnO2 nanotubes functionalized with Co3O4 nanoparticles and their use as bifunctional air cathode catalysts for oxygen reduction reaction and oxygen evolution reaction in rechargeable zinc-air batteries. These hybrid MnO2/Co3O4 nanomaterials exhibit enhanced catalytic reactivity toward oxygen evolution reaction under alkaline conditions compared with that in the presence of MnO2 nanotubes or Co3O4 nanoparticles alone. Electronic supplementary information (ESI) available: Zinc-air cell device, XPS survey scan and power density of the cell. See DOI: 10.1039/c3nr00300k

  8. A new concept for high-cycle-life LEO: Rechargeable MnO2-hydrogen

    NASA Technical Reports Server (NTRS)

    Appleby, A. John; Dhar, Y. J.; Murphy, O. J.; Srinivasan, Supramaniam

    1989-01-01

    The nickel-hydrogen secondary battery system is now the one of choice for use in GEO satellites. It offers superior energy density to that of nickel-cadmium, with a lifetime that is at least comparable in terms of both cycle life and overall operating life. While the number of deep cycles required for GEO use is small, LEO satellites with long lifetimes (5 to 10 years) will require secondary battery systems allowing 30,000 to 60,000 useful cycles which are characterized by an approximately 2C charge rate and C average discharge rate. Recent work has shown that birnessite MnO2 doped with bismuth oxide can be cycled at very high rates (6C) over a very large number of cycles (thousands) at depths-of-discharge in the 85 to 90 percent range, based on two electrons, which discharge at the same potential in a flat plateau. The potential is about 0.7 V vs. hydrogen, with a cut-off at 0.6 V. At first sight, this low voltage would seem to be a disadvantage, since the theoretical energy density will be low. However, it permits the use of lightweight materials that are immune from corrosion at the positive. The high utilization and low equivalent weight of the active material, together with the use of teflon-bonded graphite for current collection, result in very light positives, especially when these are compared with those in a derated nickel-hydrogen system. In addition, the weight of the pressure vessel falls somewhat, since the dead volume is lower. Calculations show that a total system will have 2.5 times the Ah capacity of a derated nickel-hydrogen LEO battery, so that the energy density, based on 1.2 V for nickel-hydrogen and 0.7 V for MnO2-hydrogen, will be 45 percent higher for comparable cycling performance.

  9. Performance of MnO2 Crystallographic Phases in Rechargeable Lithium-Air Oxygen Cathode

    NASA Astrophysics Data System (ADS)

    Oloniyo, Olubukun; Kumar, Senthil; Scott, Keith

    2012-05-01

    Manganese dioxide (MnO2) has been shown to be effective for improving the efficiency of cathodes in lithium-air cells. Different crystallographic phases including α-, β-, and γ-MnO2 nanowires, α-MnO2 nanospheres, and α-MnO2 nanowires on carbon ( α-MnO2/C) were synthesized using the hydrothermal method. Their physical properties were examined using x-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area measurements, and scanning electron microscopy (SEM) and found to be in agreement with the literature. Electrochemical properties of the synthesized catalyst particles were investigated by fabricating cathodes and testing them in a lithium-air cell with lithium hexafluorophosphate in propylene carbonate (LiPF6/PC) and tetra(ethylene glycol)dimethyl ether (LiTFSi/TEGDME) electrolytes. α-MnO2 had the highest discharge capacity in the LiTFSi/TEGDME electrolyte (2500 mAh/g), whilst α-MnO2/C in LiPF6/PC showed a significantly higher discharge capacity of 11,000 mAh/g based on total mass of the catalytic cathode. However, the latter showed poor capacity retention compared with γ-MnO2 nanowires, which was stable for up to 30 cycles. The reported discharge capacity is higher than recorded in previous studies on lithium-air cells.

  10. Preparation and adsorption performance of MnO2/PAC composite towards aqueous glyphosate.

    PubMed

    Cui, Hao; Li, Qin; Qian, Yan; Zhang, Qiu; Zhai, Jianping

    2012-09-01

    Glyphosate (N-phosphonomethylglycine (PMG)) is the organophosphate herbicide most widely used in the world, and industrial production of PMG generates large quantities of wastewater. A manganese dioxide-coated powdered activated carbon (MnO2/PAC) composite was synthesized and investigated for the adsorption of PMG from wastewater. The results of scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectrometry (EDAX) revealed that MnO2 was formed on the surface of the carbon during the modification process. Batch adsorption results showed that the optimal pH for glyphosate adsorption on MnO2/PAC was 3.0. In the range 0.01(-1) molL(-1), glyphosate removal by MnO2/PAC decreased with an increase in ionic strength. Among the coexistent anions, only phosphate showed significant inhibition of PMG removal due to competitive complexation. Batch studies revealed that MnO2/PAC could reach a maximum PMG adsorption capacity of 283 mg g(-1). The Langmuir equilibrium model was found to be suitable for describing PMG sorption, and kinetic studies revealed that adsorption followed second-order rate kinetics. It was also proved that the adsorbed PMG could be effectively desorbed from MnO2/PAC in 1.0 molL(-1) NaOH. All of these results implied that the MnO2/PAC composite may be used as an effective adsorbent for recycling PMG from wastewater. PMID:23240199

  11. Hollow K0.27MnO2 Nanospheres as Cathode for High-Performance Aqueous Sodium Ion Batteries.

    PubMed

    Liu, Yang; Qiao, Yun; Lou, Xiangdong; Zhang, Xinhe; Zhang, Wuxing; Huang, Yunhui

    2016-06-15

    Hollow K0.27MnO2 nanospheres as cathode material were designed for aqueous sodium ion batteries (SIBs) using polystyrene (PS) as a template. The samples were systematically studied by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. As cathode materials for aqueous SIBs, the hollow structure can effectively improve the sodium storage property. A coin cell with hollow K0.27MnO2 as cathode and NaTi2(PO4)3 as anode exhibits a specific capacity of 84.9 mA h g(-1) at 150 mA g(-1), and the capacity of 56.6 mA h g(-1) is still maintained at an extremely high current density of 600 mA g(-1). For full cell measurement at the current density of 200 mA g(-1), 83% capacity retention also can be attained after 100 cycles. The as-designed hollow K0.27MnO2 nanospheres demonstrate long cyclability and high rate capability, which grant the potential for application in advanced aqueous SIBs. PMID:27229291

  12. Removal of Cr(VI) from aqueous solutions by adsorption on MnO2.

    PubMed

    Gheju, Marius; Balcu, Ionel; Mosoarca, Giannin

    2016-06-01

    Adsorption of Cr(VI) on MnO2 was investigated with respect to effect of pH, temperature, ionic strength, initial Cr(VI) concentration, co-presence of different anions (HCO3(-), SO4(2-), H2PO4(-), NO3(-) and Cl(-)) and of low molecular weight natural organic materials (LMWNOM) (acetate, oxalate and citrate). The process was rapid during the first 3-5min, reaching equilibrium after one hour. Adsorption decreased with increasing pH, temperature and Cr(VI) initial concentration, and increased with increasing ionic strength. Co-presence of phosphate, sulfate, bicarbonate, citrate and oxalate hindered Cr(VI) adsorption, whereas nitrate, chloride and acetate did not exert any notable influence. The overall order of Cr(VI) adsorption suppression due to co-presence of anions and LMWNOM was H2PO4(-)>HCO3(-)>SO4(2-), and oxalate>citrate, respectively. Highest experimental equilibrium sorption capacity (0.83mgg(-1)) was obtained at 20°C and pH 5.9, while lowest (0.18mgg(-1)) was noticed in the co-presence of H2PO4(-), at 20°C and pH 6.9. Adsorption kinetics was successfully fitted by pseudo-second-order model. Mechanisms for both specific and non-specific adsorption are likely to be involved, while rate-controlling step involved both intra-particle and film diffusion processes. Cr(VI) was strongly bound to MnO2, which makes risks of its subsequent liberation into the environment to be low. PMID:26947189

  13. Fe3O4 and MnO2 assembled on honeycomb briquette cinders (HBC) for arsenic removal from aqueous solutions.

    PubMed

    Zhu, Jin; Baig, Shams Ali; Sheng, Tiantian; Lou, Zimo; Wang, Zhuoxing; Xu, Xinhua

    2015-04-01

    In this study, a novel composite adsorbent (HBC-Fe3O4-MnO2) was synthesized by combining honeycomb briquette cinders (HBC) with Fe3O4 and MnO2 through a co-precipitation process. The purpose was to make the best use of the oxidative property of MnO2 and the adsorptive ability of magnetic Fe3O4 for enhanced As(III) and As(V) removal from aqueous solutions. Experimental results showed that the adsorption capacity of As(III) was observed to be much higher than As(V). The maximum adsorption capacity (2.16 mg/g) was achieved for As(III) by using HBC-Fe3O4-MnO2 (3:2) as compared to HBC-Fe3O4-MnO2 (2:1) and HBC-Fe3O4-MnO2 (1:1). The experimental data of As(V) adsorption fitted well with the Langmuir isotherm model, whereas As(III) data was described perfectly by Freundlich model. The pseudo-second-order kinetic model was fitted well for the entire adsorption process of As(III) and As(V) suggesting that the adsorption is a rate-controlling step. Aqueous solution pH was found to greatly affect the adsorption behavior. Furthermore, co-ions including HCO3(-) and PO4(3-) exhibited greater influence on arsenic removal efficiency, whereas Cl(-), NO3(-), SO4(2-) were found to have negligible effects on arsenic removal. Five consecutive adsorption-regeneration cycles confirmed that the adsorbent could be reusable for successive arsenic treatment and can be used in real treatment applications. PMID:25585269

  14. Nanowire Na0.35MnO2 from a hydrothermal method as a cathode material for aqueous asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Zhang, B. H.; Liu, Y.; Chang, Z.; Yang, Y. Q.; Wen, Z. B.; Wu, Y. P.; Holze, R.

    2014-05-01

    Nanowire Na0.35MnO2 was prepared by a simple and low energy consumption hydrothermal method; its electrochemical performance as a cathode material for aqueous asymmetric supercapacitors in Na2SO4 solution was investigated. Due to the nanowire structure its capacitance (157 F g-1) is much higher than that of the rod-like Na0.95MnO2 (92 F g-1) from solid phase reaction although its sodium content is lower. When it is assembled into an asymmetric aqueous supercapacitor using activated carbon as the counter electrode and aqueous 0.5 mol L-1 Na2SO4 electrolyte solution, the nanowire Na0.35MnO2 shows an energy density of 42.6 Wh kg-1 at a power density of 129.8 W kg-1 based on the total weight of the two electrode material, higher than those for the rod-like Na0.95MnO2, with an energy density of 27.3 Wh kg-1 at a power density of 74.8 W kg-1, and that of LiMn2O4. The new material presents excellent cycling behavior even when dissolved oxygen is not removed from the electrolyte solution. The results hold great promise for practical applications of this cathode material since sodium is much cheaper than lithium and its natural resources are rich.

  15. Ti-substituted tunnel-type Na0.44MnO2 oxide as a negative electrode for aqueous sodium-ion batteries

    DOE PAGESBeta

    Wang, Yuesheng; Liu, Jue; Lee, Byungju; Qiao, Ruimin; Yang, Zhenzhong; Xu, Shuyin; Yu, Xiqian; Gu, Lin; Hu, Yong-Sheng; Yang, Wanli; et al

    2015-03-25

    The aqueous sodium-ion battery system is a safe and low-cost solution for large-scale energy storage, due to the abundance of sodium and inexpensive aqueous electrolytes. Although several positive electrode materials, e.g., Na0.44MnO2, were proposed, few negative electrode materials, e.g., activated carbon and NaTi2(PO4)3, are available. Here we show that Ti-substituted Na0.44MnO2 (Na0.44[Mn1-xTix]O2) with tunnel structure can be used as a negative electrode material for aqueous sodium-ion batteries. This material exhibits superior cyclability even without the special treatment of oxygen removal from the aqueous solution. Atomic-scale characterizations based on spherical aberration-corrected electron microscopy and ab initio calculations are utilized to accuratelymore » identify the Ti substitution sites and sodium storage mechanism. Ti substitution tunes the charge ordering property and reaction pathway, significantly smoothing the discharge/charge profiles and lowering the storage voltage. Both the fundamental understanding and practical demonstrations suggest that Na0.44[Mn1-xTix]O2 is a promising negative electrode material for aqueous sodium-ion batteries.« less

  16. Inorganic rechargeable non-aqueous cell

    SciTech Connect

    Bowden, William L.; Dey, Arabinda N.

    1985-05-07

    A totally inorganic non-aqueous rechargeable cell having an alkali or alkaline earth metal anode such as of lithium, a sulfur dioxide containing electrolyte and a discharging metal halide cathode, such as of CuCl.sub.2, CuBr.sub.2 and the like with said metal halide being substantially totally insoluble in SO.sub.2 and admixed with a conductive carbon material.

  17. Advances of aqueous rechargeable lithium-ion battery: A review

    NASA Astrophysics Data System (ADS)

    Alias, Nurhaswani; Mohamad, Ahmad Azmin

    2015-01-01

    The electrochemical characteristic of the aqueous rechargeable lithium-ion battery has been widely investigated in efforts to design a green and safe technology that can provide a highly specific capacity, high efficiency and long life for high power applications such as the smart grid and electric vehicle. It is believed that the advantages of this battery will overcome the limitations of the rechargeable lithium-ion battery with organic electrolytes that comprise safety and create high fabrication cost issues. This review focuses on the opportunities of the aqueous rechargeable lithium-ion battery compared to the conventional rechargeable lithium-ion battery with organic-based electrolytes. Previously reported studies are briefly summarised, together with the presentation of new findings based on the conductivity, morphology, electrochemical performance and cycling stability results. The factors that influence the electrochemical performance, the challenges and potential of the aqueous rechargeable lithium-ion battery are highlighted in order to understand and maintained the excellent battery performance.

  18. Reaction of aqueous Cu-Citrate with MnO2 birnessite: characterization of Mn dissolution, oxidation products and surface interactions.

    PubMed

    Jefferson, William A; Hu, Chengzhi; Liu, Huijuan; Qu, Jiuhui

    2015-01-01

    Citric acid, a widespread soil rhizosphere plant/microbe carboxylic acid exudate can easily form chelates with heavy metals, increasing their availability in the environment. When Cu(II) from algal control in water bodies or reservoirs and fungicides, such as the Bordeaux mixture, and citrate interact, solubilization through chelation is a possible outcome. Manganese (hydr)oxides represent a significant portion of the subsurface environment and can affect the fate and transport of chemical species through adsorption and oxidation. This study explores the possible interaction between MnO2 and Cu-Citrate under ambient oxic conditions. The calculated Mn(II) dissolution rates during the initial 1h of reaction followed the series Cu(II)>Cu-Citrate 1:0.5>Cu-Citrate 1:1(oxic)>Citrate>Cu-Citrate 1:1(Anoxic), reinforcing the central role of (complexed or un-complexed) Cu(II) during the initial surface-coordination instead of following the s-shaped auto-catalytic curves of Mn(II) dissolution in citrate solution. The use of capillary electrophoresis allowed the detection of an intermediate Cu(II)Acetonedicarboxylate complex and the oxidation products acetonedicarboxylate, acetoacetate, acetone and acetic acid. The mass balance analysis of Cu-Citrate 1:1 suggests the partial adsorption of Cu-Citrate(ads) and catalytic degradation of acetonedicarboxylate through a MnO2-Cu surface sorbed complex. Lastly, XPS analysis confirmed the MnO2 surface Cu(II) reduction along with an outer-hydration layer at the MnO2 interface, where electron transfer and aquo ligand exchange may lead to the oxidation of Cu-Citrate. PMID:25460741

  19. A rechargeable Na-Zn hybrid aqueous battery fabricated with nickel hexacyanoferrate and nanostructured zinc

    NASA Astrophysics Data System (ADS)

    Lu, Ke; Song, Bin; Zhang, Jintao; Ma, Houyi

    2016-07-01

    Rechargeable aqueous batteries are very attractive as a promising alternative energy storage system, although their reversible capacity is typically limited. A new rechargeable Na-Zn hybrid aqueous battery with nickel hexacyanoferrate (NiHCF) cathode and the nanostructured zinc anode is fabricated. The rational combination of two materials with mild aqueous electrolyte renders the devices with an average operating voltage close to 1.5 V, higher specific capacity of 76.2 mAh g-1, and a good cycling stability with 81% capacity retention for 1000 cycles. These remarkable features can provide guidance for the development of rechargeable batteries from the naturally abundant electrode materials with neutral aqueous electrolytes.

  20. Silicon anode for rechargeable aqueous lithium-air batteries

    NASA Astrophysics Data System (ADS)

    Teranishi, R.; Si, Q.; Mizukoshi, F.; Kawakubo, M.; Matsui, M.; Takeda, Y.; Yamamoto, O.; Imanishi, N.

    2015-01-01

    A novel aqueous lithium-air rechargeable cell with the configuration of Si/1 M LiClO4 in ethylene carbonate-diethylene carbonate/Li1+x+yAlx(Ti,Ge)2-xP3-ySiyO12/5 M LiCl-1 M LiOH aqueous solution/carbon black, air is proposed. A silicon anode composed of mechanically milled silicon power with an average particle size of ca. 0.5 μm, vapor grown carbon fiber and a polyimide binder was examined. The open-circuit voltage at the charged state was 2.9 V at 25 °C. The discharge capacity of 700 mAh g-silicon-1 was retained for 40 cycles at 0.3 mA cm-2 with cut-off voltages of 3.5 and 1.5 V. Significant capacity fade was observed at deep charge and discharge cycling at 2000 mAh g-silicon-1.

  1. Aqueous Rechargeable Zinc/Aluminum Ion Battery with Good Cycling Performance.

    PubMed

    Wang, Faxing; Yu, Feng; Wang, Xiaowei; Chang, Zheng; Fu, Lijun; Zhu, Yusong; Wen, Zubiao; Wu, Yuping; Huang, Wei

    2016-04-13

    Developing rechargeable batteries with low cost is critically needed for the application in large-scale stationary energy storage systems. Here, an aqueous rechargeable zinc//aluminum ion battery is reported on the basis of zinc as the negative electrode and ultrathin graphite nanosheets as the positive electrode in an aqueous Al2(SO4)3/Zn(CHCOO)2 electrolyte. The positive electrode material was prepared through a simple electrochemically expanded method in aqueous solution. The cost for the aqueous electrolyte together with the Zn negative electrode is low, and their raw materials are abundant. The average working voltage of this aqueous rechargeable battery is 1.0 V, which is higher than those of most rechargeable Al ion batteries in an ionic liquid electrolyte. It could also be rapidly charged within 2 min while maintaining a high capacity. Moreover, its cycling behavior is also very good, with capacity retention of nearly 94% after 200 cycles. PMID:26716878

  2. Hydrogen peroxide sensing at MnO2/carbonized nanostructured polyaniline electrode

    NASA Astrophysics Data System (ADS)

    Šljukić, B.; Stojković, I.; Cvijetićanin, N.; Ćirić-Marjanović, G.

    2011-12-01

    Manganese dioxide modified carbonized nanostructured polyaniline (MnO2/Carb-nanoPANI) was prepared via a novel hydrothermal procedure. The synthesized material was characterized using XRD, SEM and TG-DTA analysis. Furthermore, MnO2/Carb-nanoPANI was examined as electrode material for potential application in the field of electroanalysis. It showed a high electrocatalytic activity for the sensing of hydrogen peroxide in an aqueous media.

  3. Recharge

    SciTech Connect

    Fayer, Michael J.

    2008-01-17

    This chapter describes briefly the nature and measurement of recharge in support of the CH2M HILL Tank Farm Vadose Zone Project. Appendix C (Recharge) and the Recharge Data Package (Fayer and Keller 2007) provide a more thorough and extensive review of the recharge process and the estimation of recharge rates for the forthcoming RCRA Facility Investigation report for Hanford single-shell tank (SST) Waste Management Areas (WMAs).

  4. Preparation of mesoporous MnO2/C catalyst for n-hexyl acetate synthesis

    NASA Astrophysics Data System (ADS)

    Yang, Zeheng; Pan, Yanmei; Mei, Zhousheng; Zhang, Weixin

    2012-03-01

    A mesoporous MnO2/C composite was prepared by impregnating self-made porous carbon spheres with manganese nitrate aqueous solution and subsequently reacting with KMnO4 aqueous solution. It was characterized with X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), the Brunauer-Emmett-Teller (BET) surface area and the Barrett-Joyner-Halenda (BJH) pore size distribution. The as-prepared mesoporous MnO2/C composite was used as catalyst for the synthesis of n-hexyl acetate, and the effects of MnO2 loading and esterification reaction parameters on the esterification rate were investigated. The results prove that MnO2 loading has a significant effect on the catalytic activity and that the mesoporous MnO2/C composite exhibits high catalytic activity with an esterification rate of 96.42% under the conditions below: MnO2 loading (73.09 wt%), catalyst dosage (0.1% in total weight), acetic acid/n-hexanol molar ratio (2:1), reaction temperature (130 °C) and reaction time (5 h).

  5. Fabrication of MnO 2-pillared layered manganese oxide through an exfoliation/reassembling and oxidation process

    NASA Astrophysics Data System (ADS)

    Yuan, Jiaqi; Liu, Zong-Huai; Qiao, Shanfeng; Ma, Xiangrong; Xu, Naicai

    MnO 2-pillared layered manganese oxide has been first fabricated by a delamination/reassembling process followed by oxidation reaction and then by heat treatment. The structural evolution of MnO 2-pillared layered manganese oxide has been characterized by XRD, SEM, DSC-GTA, IR and N 2 adsorption-desorption. MnO 2-pillared layered manganese oxide shows a relative high thermal stability and mesoporous characteristic. The layered structure with a basal spacing of 0.66 nm could be maintained up to 400 °C. The electrochemical properties of the synthesized MnO 2-pillared layered manganese oxide have been studied using cyclic voltammetry in a mild aqueous electrolyte. Sample MnO 2-BirMO (300 °C) shows good capacitive behavior and cycling stability, and the specific capacitance value is 206 F g -1.

  6. Porous MnO2 prepared by sol-gel method for electrochemical supercapacitor

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Kumar, A.; Jayakumar, O. D.; Nazri, G. A.; Naik, V. M.; Naik, R.

    2015-03-01

    MnO2 has attracted great attention as material for electrochemical pseudocapacitor due to its high theoretical specific faradic capacitance (~ 1370 F .g-1) , environmental friendliness and wide potential window in both aqueous and nonaqueous electrolytes. However, the MnO2 has a low surface area which depresses its electrochemical performance. The amorphous α-MnO2 composite was synthesized by sol gel method in the presence of the tri-block copolymer P123. Our aim is to investigate the role of P123 on the electrochemical performance of MnO2. The samples with and without P123 were prepared and characterized by x-ray diffraction (XRD), SEM, TEM and Brunauer-Emmett-Teller (BET) method. The electrochemical performances of the amorphous MnO2 composites as the electrode materials for supercapacitors were evaluated by cyclic voltammetry and AC impedance measurements in a 1M Na2SO4 solution. The results show that the sample prepared without P123 exhibited a relatively low specific capacitance of 28F .g-1, whereas the porous MnO2 prepared with P123 exhibited 117 F .g-1at 5 mV/s. The results of crystalline MnO2 composites will also be presented. The authors acknowledge the support from the Richard J. Barber Foundation for Interdisciplinary Research.

  7. Structure and Manufacturing Process of MnO2 Counter Electrode in Niobium Suboxide Capacitors

    NASA Astrophysics Data System (ADS)

    Chen, Liqin; Li, Bo; Qi, Zhaoxiong; Guo, Hai; Zhou, Ji; Li, Longtu

    2013-10-01

    The influence of iterative heat treatment of impregnated aqueous Mn(NO3)2 solution on the microstructure of the produced MnO2 has been investigated in the fabrication process for niobium suboxide capacitors. We separate the whole process into two stages: At the early stage of impregnations in Mn(NO3)2 solution (with specific density less than 1.35 g/cm3), the produced MnO2 grains with equiaxed nanocrystalline morphology are mainly located in the inner space and pores, avoiding the performance deterioration due to the electrical conductivity anisotropy of columnar texture in NbO capacitors. For impregnation in Mn(NO3)2 solutions with specific density greater than 1.35 g/cm3, MnO2 grains in the inner space and pores continue to grow and present a hexagonal pyramid shape. At this stage, MnO2 starts to be produced on the outer surface of pellets and exhibits a cluster morphology that consists of MnO2 grains with size between 30 nm and 80 nm. The electrical performance of NbO capacitors has been optimized by adjusting the impregnation times and sequence. By alternately impregnating in Mn(NO3)2 solutions with specific densities of 1.23 g/cm3 and 1.35 g/cm3, MnO2 grains are better combined and the internal space of the pellets is fully filled. Impregnation in Mn(NO3)2 solutions with low specific densities (1.10 g/cm3 and 1.23 g/cm3) in dry atmosphere produces a denser MnO2 layer in the internal space, leading to improved capacitor performance.

  8. Design and Preparation of MnO2/CeO2-MnO2 Double-Shelled Binary Oxide Hollow Spheres and Their Application in CO Oxidation.

    PubMed

    Zhang, Jian; Cao, Yidan; Wang, Chang-An; Ran, Rui

    2016-04-01

    Herein, we designed an extremely facile method to prepare well-defined MnO2@CeO2-MnO2 ball-in-ball binary oxide hollow spheres by employing carbon spheres (CSs) as sacrificial templates. The synthesis process involves a novel self-assembled approach to prepare core-shell CSs@CeO2 precursor, which would directly react with KMnO4 aqueous solution to form yolk-shell CSs@MnO2/CeO2-MnO2 precursor in the following step. Well-dispersed Ce-Mn binary oxide with double-shelled hollow sphere structure could be achieved after annealing the precursor in air. The evolution process and formation mechanism of this novel structure were thoroughly studied in this paper. Especially the as-prepared double-shell MnO2/CeO2-MnO2 hollow spheres exhibited enhanced catalytic activity for CO oxidation compared with the pure MnO2 hollow spheres and pure CeO2 hollow spheres. We believe the high surface area, hierarchical porous structures, and strong synergistic interaction between CeO2 and MnO2 contribute to the excellent catalytic activity. Most importantly, this method could be extended to prepare other transition metal oxides. As an example, triple-shelled Co-Mn composite hollow spheres assembled by ultrathin nanoplates were successfully prepared. PMID:26998672

  9. Synthesis and characterization of different MnO2 morphologies for lithium-air batteries

    NASA Astrophysics Data System (ADS)

    Choi, Hyun-A.; Jang, Hyuk; Hwang, Hyein; Choi, Mincheol; Lim, Dongwook; Shim, Sang Eun; Baeck, Sung-Hyeon

    2014-09-01

    Manganese dioxide (MnO2) was synthesized in the forms of nanorods, nanoparticles, and mesoporous structures and the characteristics of these materials were investigated. Crystallinities were studied by x-ray diffraction and morphologies by scanning and transmission electron microscopy. Average pore sizes and specific surface areas were analyzed using the Barret-Joyner-Halenda and Brunauer-Emmett-Teller methods, respectively. Samples were also studied by cyclic voltammetry using 1M aqueous KOH solution saturated with either O2 or N2 as electrolytes to investigate their ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) activities. Of the samples produced, mesoporous MnO2 exhibited the highest ORR and OER catalytic activities. Mesoporous MnO2 supported on a gas diffusion layer was also used as a catalyst on the air electrode (cathode) of a lithium-air battery in organic electrolyte. The charge-discharge behavior of mesoporous MnO2 was investigated at a current density 0.2 mAcm-2 in a pure oxygen environment. Mesoporous MnO2 electrodes showed stable cycleability up to 65 cycles at a cell capacity of 700 mAhg-1.

  10. Hierarchical MnO2 Spheres Decorated by Carbon-Coated Cobalt Nanobeads: Low-Cost and High-Performance Electrode Materials for Supercapacitors.

    PubMed

    Zhi, Jian; Reiser, Oliver; Huang, Fuqiang

    2016-04-01

    MnO2 is a promising electrode material for supercapacitors, because it exhibits high theoretical specific capacitance (1380 F g(-1)) for electrical charge while also being inexpensive and environmentally benign. However, owing to its low electrical conductivity, the intrinsic pseudocapacity of MnO2 is not fully utilized. In this work, hierarchically structured spheres composed of MnO2 nanoplatelets and carbon coated cobalt nanobeads (MnO2-NPs@Co/C) are chosen as electrode materials for supercapacitor. With a Co/C mass loading of 19 wt %, the electrical conductivity of the hybrid is 122-fold larger than that of pristine MnO2, showing a specific capacitance of the constituent MnO2 as high as 1240 F g(-1), being close to the theoretical value. Such improved specific capacitance of MnO2-NPs@Co/C electrode is largely contributed from the enhanced double-layer charging and Faradaic pseudocapacity of MnO2. Moreover, the fabricated symmetrical supercapacitor also exhibits excellent cycling stability with 89.1% capacitance retention over 10000 cycles, as well as high energy densities in both aqueous and organic electrolyte (24 Wh kg(-1) and 33 W kg(-1), respectively). Compared with frequently used noble metals to enhance the electrochemical performance of MnO2, the utilization of low cost Co/C nanobeads is proven to be more efficient and thus showing great potential for commercial application. PMID:26987041

  11. Exploration of cobalt phosphate as a potential catalyst for rechargeable aqueous sodium-air battery

    NASA Astrophysics Data System (ADS)

    Senthilkumar, Baskar; Khan, Ziyauddin; Park, Sangmin; Seo, Inseok; Ko, Hyunhyub; Kim, Youngsik

    2016-04-01

    Bifunctional catalysts are prominent to attain high capacity, maximum energy efficiency and long cycle-life for aqueous rechargeable Na-air batteries. In this work, we report the synthesis of bi-functional noble metal free, Co3(PO4)2 nanostructures by facile precipitation technique and evaluated its electrocatalytic activity. Co3(PO4)2 nanostructure was investigated as a potential electrocatalyst for rechargeable aqueous Na-air battery for the first time. The synthesized Co3(PO4)2 grain-like nanostructures showed better oxygen evolution activity compared to Pt/C catalyst. The fabricated Na-air battery with the Co3(PO4)2 catalyst as air-cathode delivered low overpotential and its round trip energy efficiency reached up to 83%. The Na-air battery exhibited stable cycle performance up to 50 cycles.

  12. Synthesis and characterizations of MnO2/multi-wall carbon nanotubes nanocomposites for lithium-air battery.

    PubMed

    Eom, Hye Ri; Kim, Min Kyung; Kim, Moon Su; Kim, Gil-Pyo; Baeck, Sung-Hyeon

    2013-03-01

    In this work, rechargeable lithium-air battery using MnO2/MWNTs nanocomposites as a catalyst was studied. MnO2/MWNTs nanocomposites were synthesized by a hydrothermal method, and their physical and chemical properties were investigated. X-ray diffraction (XRD) was used to examine crystallinity and morphology was investigated by transmission electron microscopy (TEM). Charge-discharge behavior and cell impedance with electrolyte replacement were investigated, and charge-discharge capacity decreased with cycles mainly due to the decomposition of carbonate-based electrolyte. PMID:23755590

  13. High voltage rechargeable magnesium batteries having a non-aqueous electrolyte

    DOEpatents

    Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E.; Hwang, Jaehee

    2016-03-22

    A rechargable magnesium battery having an non-aqueous electrolyte is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

  14. Growth of One-Dimensional MnO2 Nanostructure

    NASA Astrophysics Data System (ADS)

    Lu, Pai; Xue, Dongfeng

    Large scale MnO2 nanorods were controllably synthesized from the inexpensive precursors (e.g., manganese acetate, ammonium persulfate) via a facile one-step low temperature hydrothermal strategy. The crystal phase and microscopic morphology of the as-prepared MnO2 nanorods were characterized by X-ray powder diffraction (XRD) and scanning electron microscope (SEM). Through investigating the morphology evolution of MnO2 products in the whole synthesis process, a novel growth mechanism of these MnO2 nanorods was proposed, which may be efficiently extended to other material systems as a general approach towards one-dimensional nanostructures. The obtained MnO2 nanorods may have potential applications in Li-ion batteries and supercapacitors.

  15. Incorporation of homogeneous, nanoscale MnO2 within ultraporous carbon structures via self-limiting electroless deposition: implications for electrochemical capacitors.

    PubMed

    Fischer, Anne E; Pettigrew, Katherine A; Rolison, Debra R; Stroud, Rhonda M; Long, Jeffrey W

    2007-02-01

    The self-limiting reaction of aqueous permanganate with carbon nanofoams produces conformal, nanoscopic deposits of birnessite ribbons and amorphous MnO2 throughout the ultraporous carbon structure. The MnO2 coating contributes additional capacitance to the carbon nanofoam while maintaining the favorable high-rate electrochemical performance inherent to the ultraporous carbon structure of the nanofoam. Such a three-dimensional design exploits the benefits of a nanoscopic MnO2-carbon interface to produce an exceptionally high area-normalized capacitance (1.5 F cm-2), as well as high volumetric capacitance (90 F cm-3). PMID:17297991

  16. Aqueous Rechargeable Alkaline CoxNi2-xS2/TiO2 Battery.

    PubMed

    Liu, Jilei; Wang, Jin; Ku, Zhiliang; Wang, Huanhuan; Chen, Shi; Zhang, Lili; Lin, Jianyi; Shen, Ze Xiang

    2016-01-26

    An electrochemical energy storage system with high energy density, stringent safety, and reliability is highly desirable for next-generation energy storage devices. Here an aqueous rechargeable alkaline CoxNi2-xS2 // TiO2 battery system is designed by integrating two reversible electrode processes associated with OH(-) insertion/extraction in the cathode part and Li ion insertion/extraction in the anode part, respectively. The prototype CoxNi2-xS2 // TiO2 battery is able to deliver high energy/power densities of 83.7 Wh/kg at 609 W/kg (based on the total mass of active materials) and good cycling stabilities (capacity retention 75.2% after 1000 charge/discharge cycles). A maximum volumetric energy density of 21 Wh/l (based on the whole packaged cell) has been achieved, which is comparable to that of a thin-film battery and better than that of typical commercial supercapacitors, benefiting from the unique battery and hierarchical electrode design. This hybrid system would enrich the existing aqueous rechargeable LIB chemistry and be a promising battery technology for large-scale energy storage. PMID:26593375

  17. MnO2-modified hierarchical graphene fiber electrochemical supercapacitor

    NASA Astrophysics Data System (ADS)

    Chen, Qing; Meng, Yuning; Hu, Chuangang; Zhao, Yang; Shao, Huibo; Chen, Nan; Qu, Liangti

    2014-02-01

    A novel hybrid fiber that MnO2 modified graphene sheets on graphene fiber has been fabricated by direct deposition of MnO2 onto graphene network surrounding graphene fiber (MnO2/G/GF). In this hierarchical structure, the graphene fiber with a sheath of 3D graphene network is coated with MnO2 nanoflowers. The 3D graphene on graphene fibers (G/GF) serves as highly conductive backbones with high surface area for deposition of nanostructured MnO2, which provide the high accessibility of electrolytic ions for shorten diffusion paths. An all-solid-state flexible supercapacitor based on a MnO2/G/GF hybrid fiber structure has been developed on the basis of the intrinsic mechanical flexibility of GF and the unique hierarchical structure. By combination of electric double layer capacitance of graphene network with the pseudocapacitance of MnO2 nanostructures, the all-solid-state fiber supercapacitor shows the much enhanced electrochemical capacitive behaviors with robust tolerance to mechanical deformation, promising for being woven into a textile for wearable electronics.

  18. An aqueous rechargeable formate-based hydrogen battery driven by heterogeneous Pd catalysis.

    PubMed

    Bi, Qing-Yuan; Lin, Jian-Dong; Liu, Yong-Mei; Du, Xian-Long; Wang, Jian-Qiang; He, He-Yong; Cao, Yong

    2014-12-01

    The formate-based rechargeable hydrogen battery (RHB) promises high reversible capacity to meet the need for safe, reliable, and sustainable H2 storage used in fuel cell applications. Described herein is an additive-free RHB which is based on repetitive cycles operated between aqueous formate dehydrogenation (discharging) and bicarbonate hydrogenation (charging). Key to this truly efficient and durable H2 handling system is the use of highly strained Pd nanoparticles anchored on graphite oxide nanosheets as a robust and efficient solid catalyst, which can facilitate both the discharging and charging processes in a reversible and highly facile manner. Up to six repeated discharging/charging cycles can be performed without noticeable degradation in the storage capacity. PMID:25382034

  19. MnO2/CeO2 for catalytic ultrasonic degradation of methyl orange.

    PubMed

    Zhao, He; Zhang, Guangming; Zhang, Quanling

    2014-05-01

    Catalytic ultrasonic degradation of aqueous methyl orange was studied in this paper. Heterogeneous catalyst MnO2/CeO2 was prepared by impregnation of manganese oxide on cerium oxide. Morphology and specific surface area of MnO2/CeO2 catalyst were characterized and its composition was determined. Results showed big differences between fresh and used catalyst. The removal efficiency of methyl orange by MnO2/CeO2 catalytic ultrasonic process was investigated. Results showed that ultrasonic process could remove 3.5% of methyl orange while catalytic ultrasonic process could remove 85% of methyl orange in 10 min. The effects of free radical scavengers were studied to determine the role of hydroxyl free radical in catalytic ultrasonic process. Results showed that methyl orange degradation efficiency declined after adding free radical scavengers, illustrating that hydroxyl free radical played an important role in degrading methyl orange. Theoretic analysis showed that the resonance size of cavitation bubbles was comparable with the size of catalyst particles. Thus, catalyst particles might act as cavitation nucleus and enhance ultrasonic cavitation effects. Measurement of H2O2 concentration in catalytic ultrasonic process confirmed this hypothesis. Effects of pre-adsorption on catalytic ultrasonic process were examined. Pre-adsorption significantly improved methyl orange removal. The potential explanation was that methyl orange molecules adsorbed on catalysts could enter cavitation bubbles and undergo stronger cavitation. PMID:24369902

  20. In Situ Correlation of Volummetric Expansion with Charge Storage in Nanostructured MnO2

    NASA Astrophysics Data System (ADS)

    Ignatova, Tetyana; Corso, Brad; Pan, Deng; Gul, O. Tolga; Collins, Phillip G.

    2015-03-01

    Pseudocapacitors aim to meet developing energy storage needs by combining the high energy density of batteries with the power performance of capacitors. However, degradation remains a critical issue for pseudocapacitor electrodes. After many cycles, nanostructured metal oxides like MnO2 lose their capacity through mechanisms that remain poorly understood. In this work, we studied the volummetric changes that accompany charge storage in nanoscale MnO2 electrodes by combining in-liquid atomic force microscopy (AFM) with 3-terminal electrochemical cycling. Typical samples consisted of thin films (100 to 400 nm) of porous, amorphous MnO2 deposited onto 2 μm2 Pt electrodes and then cycled in aqueous LiClO4 electrolyte. In situ measurements of film expansion during charge insertion observed 3.6% volummetric expansion for partial charging of 0.1 electron per Mn atom over a wide range of scan rates and voltage windows, even though these parameters change the balance between fast, double-layer capacitance and bulk, redox pseudocapacitance mechanisms. In fact, volume expansion is universally attributed to bulk charging, so the invariance highlights an unexpected role for surface processes in nanostructured electrode materials.

  1. Rechargeable aqueous lithium-air batteries with an auxiliary electrode for the oxygen evolution

    NASA Astrophysics Data System (ADS)

    Sunahiro, S.; Matsui, M.; Takeda, Y.; Yamamoto, O.; Imanishi, N.

    2014-09-01

    A rechargeable aqueous lithium-air cell with a third auxiliary electrode for the oxygen evolution reaction was developed. The cell consists of a lithium metal anode, a lithium conducting solid electrolyte of Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12, a carbon black oxygen reduction air electrode, a RuO2 oxygen evolution electrode, and a saturated aqueous solution of LiOH with 10 M LiCl. The cell was successfully operated for several cycles at 0.64 mA cm-2 and 25 °C under air, where the capacity of air electrode was 2000 mAh gcathod-1. The cell performance was degraded gradually by cycling under open air. The degradation was reduced under CO2-free air and pure oxygen. The specific energy density was calculated to be 810 Wh kg-1 from the weight of water, lithium, oxygen, and carbon in the air electrode.

  2. An Aqueous Rechargeable Lithium Battery Using Coated Li Metal as Anode

    PubMed Central

    Wang, Xujiong; Hou, Yuyang; Zhu, Yusong; Wu, Yuping; Holze, Rudolf

    2013-01-01

    New energy industry including electric vehicles and large-scale energy storage in smart grids requires energy storage systems of good safety, high reliability, high energy density and low cost. Here a coated Li metal is used as anode for an aqueous rechargeable lithium battery (ARLB) combining LiMn2O4 as cathode and 0.5 mol l−1 Li2SO4 aqueous solution as electrolyte. Due to the “cross-over” effect of Li+ ions in the coating, this ARLB delivers an output voltage of about 4.0 V, a big breakthrough of the theoretic stable window of water, 1.229 V. Its cycling is very excellent with Coulomb efficiency of 100% except in the first cycle. Its energy density can be 446 Wh kg−1, about 80% higher than that for traditional lithium ion battery. Its power efficiency can be above 95%. Furthermore, its cost is low and safety is much reliable. It provides another chemistry for post lithium ion batteries. PMID:23466633

  3. An aqueous rechargeable lithium battery using coated Li metal as anode.

    PubMed

    Wang, Xujiong; Hou, Yuyang; Zhu, Yusong; Wu, Yuping; Holze, Rudolf

    2013-01-01

    New energy industry including electric vehicles and large-scale energy storage in smart grids requires energy storage systems of good safety, high reliability, high energy density and low cost. Here a coated Li metal is used as anode for an aqueous rechargeable lithium battery (ARLB) combining LiMn2O4 as cathode and 0.5 mol l(-1) Li2SO4 aqueous solution as electrolyte. Due to the "cross-over" effect of Li(+) ions in the coating, this ARLB delivers an output voltage of about 4.0 V, a big breakthrough of the theoretic stable window of water, 1.229 V. Its cycling is very excellent with Coulomb efficiency of 100% except in the first cycle. Its energy density can be 446 Wh kg(-1), about 80% higher than that for traditional lithium ion battery. Its power efficiency can be above 95%. Furthermore, its cost is low and safety is much reliable. It provides another chemistry for post lithium ion batteries. PMID:23466633

  4. Experimental and mathematical studies on cycle life of rechargeable hybrid aqueous batteries

    NASA Astrophysics Data System (ADS)

    Han, Zhixu; Askhatova, Diana; Doan, The Nam Long; Hoang, Tuan K. A.; Chen, P.

    2015-04-01

    Rechargeable hybrid aqueous batteries (ReHABs) were constructed from LiMn2O4 cathode, aqueous electrolyte containing ZnSO4 and Li2SO4, and polished zinc foil anode. Cyclability data were obtained from a Neware battery tester and the data were modeled by the particle filter method. This method exhibits superior performance in both tracking and predicting the cyclability behavior of ReHABs. Data from both Swagelok and coin cells are modeled successfully and the results show that the non-linear term in the model of Swagelok batteries is larger than that in the model of coin cells. This nonlinear term is varied versus battery types. This fact shows the versatility of the particle filter method in modeling different types of batteries. This finding is crucial because it proves the suitability of particle filter method as a promising candidate in the evaluation of battery cycle life, without the need for running batteries till the end of life, which may take up to a few thousands of cycles and last for several months or years.

  5. Highly conductive three-dimensional MnO2-carbon nanotube-graphene-Ni hybrid foam as a binder-free supercapacitor electrode.

    PubMed

    Zhu, Guoyin; He, Zhi; Chen, Jun; Zhao, Jin; Feng, Xiaomiao; Ma, Yanwen; Fan, Quli; Wang, Lianhui; Huang, Wei

    2014-01-21

    Carbon nanotube (CNT)-graphene hybrids grown on porous Ni foam are used as substrates to immobilize MnO2 nanoflakes, thus forming three-dimensional (3D) MnO2-CNT-graphene-Ni hybrid foam. The as-prepared hybrid materials could be used as supercapacitor electrodes directly without any binder and conductive additives, and fully maintain the high conductivity and high surface-to-volume ratio of CNTs, large pseudocapacitance of MnO2 nanoflakes and high porosity provided by the framework of Ni foam. The conductivity of the 3D MnO2-CNT-graphene-Ni foam is as high as 117 S cm(-1) due to the seamless integration of MnO2 nanoflakes, CNTs, graphene and Ni foam among the 3D frameworks, which guarantee its low internal resistance (1.25 ohm) when compacted into supercapacitor devices. In aqueous electrolytes, the 3D MnO2-CNT-graphene-Ni based prototype supercapacitors show specific capacitances of ~251 F g(-1) with good cycling stability at a current density of 1.0 A g(-1). In addition, these 3D hybrids also demonstrate their potential in all-solid-state flexible supercapacitors. PMID:24296659

  6. Hydrothermal synthesis of MnO2/CNT nanocomposite with a CNT core/porous MnO2 sheath hierarchy architecture for supercapacitors

    PubMed Central

    2012-01-01

    MnO2/carbon nanotube [CNT] nanocomposites with a CNT core/porous MnO2 sheath hierarchy architecture are synthesized by a simple hydrothermal treatment. X-ray diffraction and Raman spectroscopy analyses reveal that birnessite-type MnO2 is produced through the hydrothermal synthesis. Morphological characterization reveals that three-dimensional hierarchy architecture is built with a highly porous layer consisting of interconnected MnO2 nanoflakes uniformly coated on the CNT surface. The nanocomposite with a composition of 72 wt.% (K0.2MnO2·0.33 H2O)/28 wt.% CNT has a large specific surface area of 237.8 m2/g. Electrochemical properties of the CNT, the pure MnO2, and the MnO2/CNT nanocomposite electrodes are investigated by cyclic voltammetry and electrochemical impedance spectroscopy measurements. The MnO2/CNT nanocomposite electrode exhibits much larger specific capacitance compared with both the CNT electrode and the pure MnO2 electrode and significantly improves rate capability compared to the pure MnO2 electrode. The superior supercapacitive performance of the MnO2/CNT nancomposite electrode is due to its high specific surface area and unique hierarchy architecture which facilitate fast electron and ion transport. PMID:24576342

  7. An aqueous rechargeable lithium battery of high energy density based on coated Li metal and LiCoO2.

    PubMed

    Wang, Xujiong; Qu, Qunting; Hou, Yuyang; Wang, Faxing; Wu, Yuping

    2013-07-14

    Using a coated Li metal as an anode and LiCoO2 as a cathode, an aqueous rechargeable battery is built up, whose average discharge voltage is 3.70 V. This high voltage stability is due to the "cross-over" effect of Li(+) ions, which is different from the traditional ways of increasing overpotentials. The total energy density can be 465 W h kg(-1). PMID:23732678

  8. Nanostructured MnO2-Based Cathodes for Li-Ion/Polymer Cells

    NASA Technical Reports Server (NTRS)

    Skandan, Ganesh; Singhal, Amit

    2005-01-01

    Nanostructured MnO2-based cathodes for Li-ion/polymer electrochemical cells have been investigated in a continuing effort to develop safe, high-energy-density, reliable, low-toxicity, rechargeable batteries for a variety of applications in NASA programs and in mass-produced commercial electronic equipment. Whereas the energy densities of state-of-the-art lithium-ion/polymer batteries range from 150 to 175 W h/kg, the goal of this effort is to increase the typical energy density to about 250 W h/kg. It is also expected that an incidental benefit of this effort will be increases in power densities because the distances over which Li ions must diffuse through nanostructured cathode materials are smaller than those through solid bulk cathode materials.

  9. N-methyl-2-pyrrolidone as a solvent for the non-aqueous electrolyte of rechargeable Li-air batteries

    NASA Astrophysics Data System (ADS)

    Wang, Hui; Xie, Kai; Wang, Lingyan; Han, Yu

    2012-12-01

    The instability of solvent molecules toward oxygen reduction species is the main reason for the performance deterioration of rechargeable Li-air batteries. Identifying the appropriate electrolyte solvents is one prerequisite for the application of Li-air batteries. In this article, we study N-methyl-2-pyrrodione (NMP) as a solvent for the non-aqueous electrolyte of Li-air batteries. Oxygen reduction reactions (ORRs) and oxygen oxidation reactions (OERs) are investigated on Au and glassy carbon (GC) electrodes in NMP-based terabutylammonium perchlorate (TBAClO4) and lithium perchlorate (LiClO4) electrolyte solutions using the cyclic voltammetry method. Raman and X-ray photoemission spectra (XPS) are used to detect the species on the electrode surface during cell cycles. The results show that while the one-electron O2/O2- reversible couples are observed in TBAClO4/NMP, in presence of Li ion, the initially formed LiO2 generated by one-electron transfer process decomposes to Li2O2. As the predominant discharge products, Li2O2 decomposes during the recharge processes. The cells using NMP-based electrolytes exhibit good cycle performance, and the first cycle efficiency is approximately 97%. Although the decomposition of NMP occurs on the air electrode surface during the cells recharge, the increased chemical stability against oxygen reduction species offer NMP-based electrolytes as potential candidates for rechargeable Li-air batteries electrolytes.

  10. High-voltage and high-rate symmetric supercapacitor based on MnO2-polypyrrole hybrid nanofilm

    NASA Astrophysics Data System (ADS)

    Wang, Chong; Zhan, Yang; Wu, Lingxia; Li, Yuanyuan; Liu, Jinping

    2014-08-01

    A manganese oxide (MnO2) nanosheet film, hybridized with a conducting polymer polypyrrole (PPy), was prepared through the direct reaction of a carbon cloth with potassium permanganate (KMnO4) and through the subsequent chemical polymerization; this type of prepared nanosheet has been used as an electrode for symmetric supercapacitors. The influence of the reaction time in the KMnO4 solution on the capacitive property of the MnO2 film was systematically investigated. Further experimentation revealed that the PPy with the high electrical conductivity had promoted the charge transfer in the MnO2 nanofilm and had played an important role in enhancing the electrode performance (˜45.6 mF cm-2). An areal capacitance of 25.9 mF cm-2 and an excellent rate performance (˜50.08% of the initial capacitance when the scan rate increases 100 times from 2.5 to 250 mV s-1) can be achieved for an aqueous symmetric supercapacitor that is assembled from the MnO2-PPy nanofilm. In particular, an operating voltage of 1.2 V can be delivered by choosing an appropriate electrolyte; this voltage level is much larger than that of traditional aqueous symmetric supercapacitors (⩽1.0 V) and contributes to a high energy density (˜3.5 μWh cm-2). Under such a high output voltage, the device can still maintain ˜86.21% of the initial capacitance, even after 2000 cycles.

  11. High-voltage and high-rate symmetric supercapacitor based on MnO2-polypyrrole hybrid nanofilm.

    PubMed

    Wang, Chong; Zhan, Yang; Wu, Lingxia; Li, Yuanyuan; Liu, Jinping

    2014-08-01

    A manganese oxide (MnO(2)) nanosheet film, hybridized with a conducting polymer polypyrrole (PPy), was prepared through the direct reaction of a carbon cloth with potassium permanganate (KMnO(4)) and through the subsequent chemical polymerization; this type of prepared nanosheet has been used as an electrode for symmetric supercapacitors. The influence of the reaction time in the KMnO(4) solution on the capacitive property of the MnO(2) film was systematically investigated. Further experimentation revealed that the PPy with the high electrical conductivity had promoted the charge transfer in the MnO(2) nanofilm and had played an important role in enhancing the electrode performance (∼45.6 mF cm(-2)). An areal capacitance of 25.9 mF cm(-2) and an excellent rate performance (∼50.08% of the initial capacitance when the scan rate increases 100 times from 2.5 to 250 mV s(-1)) can be achieved for an aqueous symmetric supercapacitor that is assembled from the MnO(2)-PPy nanofilm. In particular, an operating voltage of 1.2 V can be delivered by choosing an appropriate electrolyte; this voltage level is much larger than that of traditional aqueous symmetric supercapacitors (≤1.0 V) and contributes to a high energy density (∼3.5 μWh cm(-2)). Under such a high output voltage, the device can still maintain ∼86.21% of the initial capacitance, even after 2000 cycles. PMID:25008287

  12. MnO 2 nanotube and nanowire arrays by electrochemical deposition for supercapacitors

    NASA Astrophysics Data System (ADS)

    Xia, Hui; Feng, Jinkui; Wang, Hailong; Lai, Man On; Lu, Li

    Highly ordered MnO 2 nanotube and nanowire arrays are successfully synthesized via a electrochemical deposition technique using porous alumina templates. The morphologies and microstructures of the MnO 2 nanotube and nanowire arrays are investigated by field emission scanning electron microscopy and transmission electron microscopy. Electrochemical characterization demonstrates that the MnO 2 nanotube array electrode has superior capacitive behaviour to that of the MnO 2 nanowire array electrode. In addition to high specific capacitance, the MnO 2 nanotube array electrode also exhibits good rate capability and good cycling stability, which makes it promising candidate for supercapacitors.

  13. An Aqueous Rechargeable Zn//Co3 O4 Battery with High Energy Density and Good Cycling Behavior.

    PubMed

    Wang, Xiaowei; Wang, Faxing; Wang, Liying; Li, Minxia; Wang, Yanfang; Chen, Bingwei; Zhu, Yusong; Fu, Lijun; Zha, Liusheng; Zhang, Lixin; Wu, Yuping; Huang, Wei

    2016-06-01

    An aqueous rechargeable Zn//Co3 O4 battery is demonstrated with Zn@carbon fibers and Co3 O4 @Ni foam as the negative and positive electrodes, respectively, using an electrolyte of 1 m KOH and 10 × 10(-3) m Zn(Ac)2 . It can operate at a cell voltage as high as 1.78 V with an energy density of 241 W h kg(-1) and presents excellent cycling. The battery is also assembled into a flexible shape, which can be applied in flexible or wearable devices requiring high energy. PMID:27120391

  14. New-concept Batteries Based on Aqueous Li+/Na+ Mixed-ion Electrolytes

    PubMed Central

    Chen, Liang; Gu, Qingwen; Zhou, Xufeng; Lee, Saixi; Xia, Yonggao; Liu, Zhaoping

    2013-01-01

    Rechargeable batteries made from low-cost and abundant materials operating in safe aqueous electrolytes are attractive for large-scale energy storage. Sodium-ion battery is considered as a potential alternative of current lithium-ion battery. As sodium-intercalation compounds suitable for aqueous batteries are limited, we adopt a novel concept of Li+/Na+ mixed-ion electrolytes to create two batteries (LiMn2O4/Na0.22MnO2 and Na0.44MnO2/TiP2O7), which relies on two electrochemical processes. One involves Li+ insertion/extraction reaction, and the other mainly relates to Na+ extraction/insertion reaction. Two batteries exhibit specific energy of 17 Wh kg−1 and 25 Wh kg−1 based on the total weight of active electrode materials, respectively. As well, aqueous LiMn2O4/Na0.22MnO2 battery is capable of separating Li+ and Na+ due to its specific mechanism unlike the traditional “rocking-chair” lithium-ion batteries. Hence, the Li+/Na+ mixed-ion batteries offer promising applications in energy storage and Li+/Na+ separation. PMID:23736113

  15. Fluorescent glutathione probe based on MnO2-phenol formaldehyde resin nanocomposite.

    PubMed

    Wang, Xudong; Wang, Dan; Guo, Yali; Yang, Chengduan; Liu, Xiaoyu; Iqbal, Anam; Liu, Weisheng; Qin, Wenwu; Yan, Dan; Guo, Huichen

    2016-03-15

    MnO2-phenol formaldehyde resin (MnO2-PFR) nanocomposite is successfully prepared by a simple chemical reduction process. The resultant MnO2-PFR nanocomposite is well characterized. The absorption band of non-fluorescent MnO2 nanosheets overlaps well with the fluorescence emission of PFR nanoparticles. The green fluorescence of PFR in this nanocomposite can be effectively quenched by fluorescence resonance energy transfer from PFR to MnO2. In the presence of glutathione (GSH), the fluorescence of PFR could be recovered due to MnO2 was reduced to Mn(2+) by GSH. The nanocomposite can be use for detecting glutathione in blood serum. PMID:26426853

  16. Synthesis and characterization of MnO 2 colloids

    NASA Astrophysics Data System (ADS)

    Yadav, Pooja; Olsson, Richard T.; Jonsson, Mats

    2009-11-01

    This work addresses the issue of radiation chemical synthesis of MnO 2 nanoparticles and also illustrates the ease of formation of nanorods and sheets by adroit manipulation of experimental conditions. The radiation chemical yield ( G-value) for reduction of Mn (VII) by the hydrated electron was found to be 0.27 μmol J -1 and 0.17 μmol J -1 respectively, when tert. butanol and isopropanol were used as scavengers in nitrogen-saturated solutions. The colloids formed upon irradiation of air-saturated solution and N 2-purged solution with tert. butanol as scavenger were found to be most stable. Irradiation of air-saturated solution containing 4×10 -4 M KMnO 4 at a dose of 1692 Gy resulted in the formation of nanorods of the dimension 100-150 nm and nanospheres in the range 10-20 nm. Irradiation of N 2-purged solution containing tert. butanol as scavenger for rad OH-produced reticulated structure of nanorods with length varying from 50 to 100 nm at a dose of 1692 Gy. Elemental analysis was performed using scanning electron microscope on MnO 2 formed by reduction and oxidation and the purity was found to be 98% of elemental Mn content.

  17. Key scientific challenges in current rechargeable non-aqueous Li-O2 batteries: experiment and theory.

    PubMed

    Bhatt, Mahesh Datt; Geaney, Hugh; Nolan, Michael; O'Dwyer, Colm

    2014-06-28

    Rechargeable Li-air (henceforth referred to as Li-O2) batteries provide theoretical capacities that are ten times higher than that of current Li-ion batteries, which could enable the driving range of an electric vehicle to be comparable to that of gasoline vehicles. These high energy densities in Li-O2 batteries result from the atypical battery architecture which consists of an air (O2) cathode and a pure lithium metal anode. However, hurdles to their widespread use abound with issues at the cathode (relating to electrocatalysis and cathode decomposition), lithium metal anode (high reactivity towards moisture) and due to electrolyte decomposition. This review focuses on the key scientific challenges in the development of rechargeable non-aqueous Li-O2 batteries from both experimental and theoretical findings. This dual approach allows insight into future research directions to be provided and highlights the importance of combining theoretical and experimental approaches in the optimization of Li-O2 battery systems. PMID:24833409

  18. Electrochemical cyclability mechanism for MnO 2 electrodes utilized as electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Wei, Weifeng; Cui, Xinwei; Chen, Weixing; Ivey, Douglas G.

    The electrochemical cyclability mechanism of nanocrystalline MnO 2 electrodes with rock salt-type and hexagonal ɛ-type structures was investigated to determine the relationship between physicochemical feature evolution and the corresponding electrochemical behaviour of MnO 2 electrodes. Rock salt MnO 2 and hexagonal ɛ-MnO 2 electrodes, with fibrous and porous morphologies, evolve into the antifluorite-type MnO 2 with a petal-shaped nanosheet structure after electrochemical cycling, similar to that observed in nanocrystalline antifluorite-type MnO 2 electrodes after electrochemical cycling. However, a different impedance response was observed for the rock salt MnO 2 and hexagonal ɛ-MnO 2 electrodes during the charge-discharge cycles, compared with the improved impedance response observed for the cycled antifluorite-type MnO 2. A dissolution-redeposition mechanism is proposed to account for the impedance response of the MnO 2 electrodes with different morphologies and crystal structures.

  19. One-pot synthesis of hierarchical MnO2-modified diatomites for electrochemical capacitor electrodes

    NASA Astrophysics Data System (ADS)

    Zhang, Yu Xin; Huang, Ming; Li, Fei; Wang, Xue Li; Wen, Zhong Quan

    2014-01-01

    The hierarchical and porous MnO2-modified diatomite structures are prepared for the first time by a one-pot hydrothermal method. The morphology and structure of MnO2-modified diatomite hierarchical structures are examined by focus ion beam scanning electron microscopy (FIB/SEM) and X-ray diffraction spectroscopy (XRD). The results show that Birnessite-type MnO2 nanosheets are observed to grow vertically on the purified diatomite, thus building hierarchical architecture. Furthermore, the electrochemical properties of the MnO2-modified diatomite electrodes are elucidated by cyclic voltammograms, galvanostatic charge/discharge tests and electrochemical impedance spectroscopy in 1 M Na2SO4 electrolyte. The electrochemical results demonstrate that the MnO2-modified diatomite electrode exhibits highly reversible features and good rate abilities, respectively. Significantly, it exhibits the specific capacitance of 202.6 F g-1 for the MnO2-modified diatomite and 297.8 F g-1 for the MnO2 nanostructures after etching the diatomite. The capacitance retention of 95.92% over 5000 cycles further indicates the suitability of the low-cost MnO2-modified diatomite structure as a potential electrode material for supercapacitors.

  20. Long-lived Aqueous Rechargeable Lithium Batteries Using Mesoporous LiTi2(PO4)3@C Anode

    NASA Astrophysics Data System (ADS)

    Sun, Dan; Tang, Yougen; He, Kejian; Ren, Yu; Liu, Suqin; Wang, Haiyan

    2015-12-01

    The instability of anode materials during cycling has been greatly limiting the lifetime of aqueous rechargeable lithium batteries (ARLBs). Here, to tackle this issue, mesoporous LiTi2(PO4)3@C composites with a pore size of 4 nm and a large BET surface area of 165 m2 g-1 have been synthesized by a novel two-step approach. The ARLB with this type of LiTi2(PO4)3@C anode, commercial LiMn2O4 cathode and 2 M Li2(SO4) aqueous solution (oxygen was removed) exhibited superior cycling stability (a capacity retention of 88.9% after 1200 cycles at 150 mA g-1 and 82.7% over 5500 cycles at 750 mA g-1) and excellent rate capability (discharge capacities of 121, 110, 90, and 80 mAh g-1 based on the mass of LiTi2(PO4)3 at 30, 150, 1500, and 3000 mA g-1, respectively). As verified, the mesoporous structure, large surface area and high-quality carbon coating layer of the LiTi2(PO4)3@C composite contribute to the breakthrough in achieving excellent electrochemical properties for ARLB.

  1. Long-lived Aqueous Rechargeable Lithium Batteries Using Mesoporous LiTi2(PO4)3@C Anode

    PubMed Central

    Sun, Dan; Tang, Yougen; He, Kejian; Ren, Yu; Liu, Suqin; Wang, Haiyan

    2015-01-01

    The instability of anode materials during cycling has been greatly limiting the lifetime of aqueous rechargeable lithium batteries (ARLBs). Here, to tackle this issue, mesoporous LiTi2(PO4)3@C composites with a pore size of 4 nm and a large BET surface area of 165 m2 g−1 have been synthesized by a novel two-step approach. The ARLB with this type of LiTi2(PO4)3@C anode, commercial LiMn2O4 cathode and 2 M Li2(SO4) aqueous solution (oxygen was removed) exhibited superior cycling stability (a capacity retention of 88.9% after 1200 cycles at 150 mA g−1 and 82.7% over 5500 cycles at 750 mA g−1) and excellent rate capability (discharge capacities of 121, 110, 90, and 80 mAh g−1 based on the mass of LiTi2(PO4)3 at 30, 150, 1500, and 3000 mA g−1, respectively). As verified, the mesoporous structure, large surface area and high-quality carbon coating layer of the LiTi2(PO4)3@C composite contribute to the breakthrough in achieving excellent electrochemical properties for ARLB. PMID:26648263

  2. Long-lived Aqueous Rechargeable Lithium Batteries Using Mesoporous LiTi2(PO4)3@C Anode.

    PubMed

    Sun, Dan; Tang, Yougen; He, Kejian; Ren, Yu; Liu, Suqin; Wang, Haiyan

    2015-01-01

    The instability of anode materials during cycling has been greatly limiting the lifetime of aqueous rechargeable lithium batteries (ARLBs). Here, to tackle this issue, mesoporous LiTi2(PO4)3@C composites with a pore size of 4 nm and a large BET surface area of 165 m(2) g(-1) have been synthesized by a novel two-step approach. The ARLB with this type of LiTi2(PO4)3@C anode, commercial LiMn2O4 cathode and 2 M Li2(SO4) aqueous solution (oxygen was removed) exhibited superior cycling stability (a capacity retention of 88.9% after 1200 cycles at 150 mA g(-1) and 82.7% over 5500 cycles at 750 mA g(-1)) and excellent rate capability (discharge capacities of 121, 110, 90, and 80 mAh g(-1) based on the mass of LiTi2(PO4)3 at 30, 150, 1500, and 3000 mA g(-1), respectively). As verified, the mesoporous structure, large surface area and high-quality carbon coating layer of the LiTi2(PO4)3@C composite contribute to the breakthrough in achieving excellent electrochemical properties for ARLB. PMID:26648263

  3. Microstructural effects on charge-storage properties in MnO2-based electrochemical supercapacitors.

    PubMed

    Ghodbane, Ouassim; Pascal, Jean-Louis; Favier, Frédéric

    2009-05-01

    The charge-storage mechanism in manganese dioxide (MnO2)-based electrochemical supercapacitors was investigated and discussed toward prepared MnO2 microstructures. The preparation of a series of MnO2 allotropic phases was performed by following dedicated synthetic routes. The resulting compounds are classified into three groups depending on their crystal structures based on 1D channels, 2D layers, or 3D interconnected tunnels. The 1D group includes pyrolusite, ramsdellite, cryptomelane, Ni-doped todorokite (Ni-todorokite), and OMS-5. The 2D and 3D groups are composed of birnessite and spinel, respectively. The prepared MnO2 powders were characterized using X-ray diffraction, scanning electron microscopy, the Brunauer-Emmett-Teller technique, cyclic voltammetry (CV), and electrochemical impedance spectroscopy. The influence of the MnO2 microstructure on the electrochemical performance of MnO2-based electrodes is commented on through the specific surface area and the electronic and ionic conductivities. It was demonstrated that the charge-storage mechanism in MnO2-based electrodes is mainly faradic rather than capacitive. The specific capacitance values are found to increase in the following order: pyrolusite (28 Fx g(-1)) < Ni-todorokite < ramsdellite < cryptomelane < OMS-5 < birnessite < spinel (241 Fx g(-1)). Thus, increasing the cavity size and connectivity results in the improvement of the electrochemical performance. In contrast with the usual assumption, the electrochemical performance of MnO2-based electrodes was not dependent on the specific surface area. The electronic conductivity was shown to have a limited impact as well. However, specific capacitances of MnO2 forms were strongly correlated with the corresponding ionic conductivities, which obviously rely on the microstructure. The CV experiments confirmed the good stability of all MnO2 phases during 500 charge/discharge cycles. PMID:20355901

  4. Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance

    NASA Astrophysics Data System (ADS)

    Zhao, H. B.; Hu, C. J.; Cheng, H. W.; Fang, J. H.; Xie, Y. P.; Fang, W. Y.; Doan, T. N. L.; Hoang, T. K. A.; Xu, J. Q.; Chen, P.

    2016-05-01

    A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g‑1 and 96 mAh g‑1 at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li+ and Na+. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0–4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries.

  5. Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance

    PubMed Central

    Zhao, H. B.; Hu, C. J.; Cheng, H. W.; Fang, J. H.; Xie, Y. P.; Fang, W. Y.; Doan, T. N. L.; Hoang, T. K. A.; Xu, J. Q.; Chen, P.

    2016-01-01

    A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g−1 and 96 mAh g−1 at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li+ and Na+. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0–4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries. PMID:27174224

  6. Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance.

    PubMed

    Zhao, H B; Hu, C J; Cheng, H W; Fang, J H; Xie, Y P; Fang, W Y; Doan, T N L; Hoang, T K A; Xu, J Q; Chen, P

    2016-01-01

    A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g(-1) and 96 mAh g(-1) at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li(+) and Na(+). The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0-4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries. PMID:27174224

  7. Investigation of the Rechargeability of Li-O2 Batteries in Non-aqueous Electrolyte

    SciTech Connect

    Xiao, Jie; Hu, Jian Z.; Wang, Deyu; Hu, Dehong; Xu, Wu; Graff, Gordon L.; Nie, Zimin; Liu, Jun; Zhang, Jiguang

    2011-07-01

    In order to understand the nature of the limited cycle life and poor energy efficiency associated with the secondary Li-O¬2 batteries the discharge products of primary Li-O2 cells at different depth of discharge (DOD) are systematically analyzed in this work. It is revealed that if discharged to 2.0 V a small amount of Li2O2 coexist with Li2CO3 and RO-(C=O)-OLi) in alkyl carbonate-based electrolyte. Further discharging the air electrodes to below 2.0 V the amount of Li2CO3 and LiRCO3 increases significantly due to the severe electrolyte decomposition. There is no Li2O detected in this alkyl carbonate electrolyte regardless of DOD. It is also found that the alkyl carbonate based electrolyte begins to decompose at 4.0 V during charging under the combined influences from the high surface area carbon, the nickel metal current collector and the oxygen atmosphere. Accordingly the impedance of the Li-O2 cell continues to increase after each discharge and recharge process indicating a repeated plating of insoluble lithium salts on the carbon surface. Therefore the whole carbon electrode becomes completely insulated only after a few cycles and loses the function of providing active tri-phase regions for the Li-oxygen batteries.

  8. Comparison of Electrodes for High-Performance Electrochemical Capacitors: Multi-Layer MnO2/Pt and Composite MnO2/Pt on Carbon Nanofibres.

    PubMed

    Lee, Yu-Jin; An, Geon-Hyoung; Ahn, Hyo-Jin

    2015-11-01

    Four different types of electrodes for high-performance electrochemical capacitors were prepared using electrospinning method and/or impregnation methods: (1) conventional carbon nanofibres (CNF) supports, and CNFs decorated with (2) MnO2 nanophases, (3) multi-layer MnO2/Pt nanophases, and (4) composite MnO2 and Pt nanophases. Their morphological, structural, chemical, and electrochemical properties were characterized using field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and galvanostatic charge/discharge measurements. Composite MnO2 and Pt nanophases decorated on the CNFs exhibited superior capacitance (-252.3 F/g at 10 mV/s), excellent capacitance retention (-93.5% after 300 cycles), and high energy densities (13.53-18.06 Wh/kg). The enhanced electrochemical performances can be explained by the composite structure, presenting well-dispersed MnO2 nanophases leading to high capacitance, and well-dispersed Pt nanophases leading to improved electrical conductivity. PMID:26726621

  9. Mixed alkali effect in glasses containing MnO2

    NASA Astrophysics Data System (ADS)

    Reddy, M. Sudhakara; Rajiv, Asha; Veeranna Gowda, V. C.; Chakradhar, R. P. S.; Reddy, C. Narayana

    2013-02-01

    Glass systems of the composition xLi2O-(25-x)K2O-70(0.4ZnO+0.6P2O5)+5MnO2 (x = 4,8,12,16 and 20 mol %) have been prepared by melt quenching technique. The thermal and mechanical properties of the glasses have been evaluated as a function of mixed alkali content. Glass transition temperature and Vickers's hardness of the glasses show a pronounced deviation from linearity at 12 mol% Li2O. Theoretically estimated elastic moduli of the glasses show small positive deviations from linearity. MAE in these properties has been attributed to the localized changes in the glass network. The absorption spectra of Mn2+ ions in these glasses showed strong broad absorption band at 514 nm corresponding to the transition 6A1g(S)→4T1g(G), characteristic of manganese ions in octahedral symmetry. The fundamental absorption edge in UV region is used to study the optical transitions and electronic band structure. From UV absorption edge, optical band gap energies have been evaluated. Band gap energies of the glasses have exhibited MAE and shows minimum value for 12 mol% Li2O glass.

  10. Advanced aqueous rechargeable lithium battery using nanoparticulate LiTi2(PO4)3/C as a superior anode

    PubMed Central

    Sun, Dan; Jiang, Yifan; Wang, Haiyan; Yao, Yan; Xu, Guoqing; He, Kejian; Liu, Suqin; Tang, Yougen; Liu, Younian; Huang, Xiaobing

    2015-01-01

    Poor cycling performance arising from the instability of anode is still a main challenge for aqueous rechargeable lithium batteries (ARLB). In the present work, a high performance LiTi2(PO4)3/C composite has been achieved by a novel and facile preparation method associated with an in-situ carbon coating approach. The LiTi2(PO4)3/C nanoparticles show high purity and the carbon layer is very uniform. When used as an anode material, the ARLB of LiTi2(PO4)3/C//LiMn2O4 delivered superior cycling stability with a capacity retention of 90% after 300 cycles at 30 mA g−1 and 84% at 150 mA g−1 over 1300 cycles. It also demonstrated excellent rate capability with reversible discharge capacities of 115 and 89 mAh g−1 (based on the mass of anode) at 15 and 1500 mA g−1, respectively. The superior electrochemical properties should be mainly ascribed to the high performance of LiTi2(PO4)3/C anode, benefiting from its nanostructure, high-quality carbon coating, appropriate crystal structure and excellent electrode surface stability as verified by Raman spectra, electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements. PMID:26035774

  11. Polypyrrole-encapsulated vanadium pentoxide nanowires on a conductive substrate for electrode in aqueous rechargeable lithium battery.

    PubMed

    Liang, Chaowei; Fang, Dong; Cao, Yunhe; Li, Guangzhong; Luo, Zhiping; Zhou, Qunhua; Xiong, Chuanxi; Xu, Weilin

    2015-02-01

    Precursors of ammonium vanadium bronze (NH4V4O10) nanowires assembled on a conductive substrate were prepared by a hydrothermal method. After calcination at 360°C, the NH4V4O10 precursor transformed to vanadium pentoxide (V2O5) nanowires, which presented a high initial capacity of 135.0mA h g(-1) at a current density of 50mA g(-1) in 5M LiNO3 aqueous solution; while the specific capacity faded quickly over 50 cycles. By coating the surface of V2O5 nanowires with water-insoluble polypyrrole (PPy), the formed nanocomposite electrode exhibited a specific discharge capacity of 89.9mA h g(-1) at 50mA g(-1) (after 100 cycles). A V2O5@PPy //LiMn2O4 rechargeable lithium battery exhibited an initial discharge capacity of 95.2mA h g(-1); and after 100 cycles, a specific discharge capacity of 81.5mA h g(-1) could retain at 100mA g(-1). PMID:25463177

  12. Advanced aqueous rechargeable lithium battery using nanoparticulate LiTi2(PO4)3/C as a superior anode.

    PubMed

    Sun, Dan; Jiang, Yifan; Wang, Haiyan; Yao, Yan; Xu, Guoqing; He, Kejian; Liu, Suqin; Tang, Yougen; Liu, Younian; Huang, Xiaobing

    2015-01-01

    Poor cycling performance arising from the instability of anode is still a main challenge for aqueous rechargeable lithium batteries (ARLB). In the present work, a high performance LiTi2(PO4)3/C composite has been achieved by a novel and facile preparation method associated with an in-situ carbon coating approach. The LiTi2(PO4)3/C nanoparticles show high purity and the carbon layer is very uniform. When used as an anode material, the ARLB of LiTi2(PO4)3/C//LiMn2O4 delivered superior cycling stability with a capacity retention of 90% after 300 cycles at 30 mA g(-1) and 84% at 150 mA g(-1) over 1300 cycles. It also demonstrated excellent rate capability with reversible discharge capacities of 115 and 89 mAh g(-1) (based on the mass of anode) at 15 and 1500 mA g(-1), respectively. The superior electrochemical properties should be mainly ascribed to the high performance of LiTi2(PO4)3/C anode, benefiting from its nanostructure, high-quality carbon coating, appropriate crystal structure and excellent electrode surface stability as verified by Raman spectra, electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements. PMID:26035774

  13. Growth and magnetic properties of MnO2-δ nanowire microspheres

    NASA Astrophysics Data System (ADS)

    Yang, J. B.; Zhou, X. D.; James, W. J.; Malik, S. K.; Wang, C. S.

    2004-10-01

    We report the synthesis of MnO2-δ microspheres using hydrothermal and conventional chemical reaction methods. The microspheres of MnO2-δ consist of nanowires having a diameter of 20-50nm and a length of 2-8μm. The value of oxygen vacancy δ estimated from x-ray photoelectron spectrum is 0.3. The magnetization versus temperature curve indicates a magnetic transition at about 13K. It is found that a parasitic ferromagnetic component is imposed on the antiferromagnetic structure of MnO2-δ, which might result from distortion of the lattice structure due to oxygen vacancies. The magnetic transition temperature TN is about 10K lower than that of the bulk MnO2 single crystal.

  14. Flexible supercapacitor based on MnO2 coated laser carbonized electrodes

    NASA Astrophysics Data System (ADS)

    Rahimi, Rahim; Ochoa, Manuel; Yu, Wuyang; Ziaie, Babak

    2015-12-01

    This paper presents a facile, low-cost approach for fabrication of flexible hybrid carbon/ MnO2 pseudo-capacitors. The highly porous carbon electrodes of the supercapacitor are fabricated by laser pyrolysis of polyimide-laminated copper sheet and subsequently coated with a uniform thin layer of MnO2. The porous laser carbonized polyimide provides a high effective surface area for the MnO2 coating, resulting in an increase of 55% in the electrochemical performance of the supercapacitor. The fabricated device exhibits a specific capacitance of 7.1mFcm-2 at a scan rate of 40mVs-1. Moreover, the copper backing film provides a proper electrical contact to the high surface area carbon/ MnO2 composite for stability under mechanical deformation and low internal resistance.

  15. A frogspawn-inspired hierarchical porous NaTi2(PO4)3-C array for high-rate and long-life aqueous rechargeable sodium batteries.

    PubMed

    Zhao, Baidan; Lin, Bo; Zhang, Sen; Deng, Chao

    2015-11-28

    Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in a hierarchical porous array, which exhibits superior mechanical strength and high-efficiency oxygen permeability. It can be used as a model for designing a new high-performance electrode material, which has advantages such as a high surface area, fast mass transport and superior durability. Herein, we report a frogspawn-like NaTi2(PO4)3/C array prepared by a facile preform impregnation strategy. The framework is formed by a hollow carbon sphere connected by the NaTi2(PO4)3/C skeleton, and its hollow is filled with the NaTi2(PO4)3 nanospheres. The whole hierarchical porous three-dimensional array copies the structure of a frogspawn. This unique structure not only enables easy electrolyte percolation and fast electron/ion transport, but also enhances the reversible capacity and cycling durability. When it is applied as an anode of the aqueous sodium ion battery, it exhibits favorable high rate capability and superior cycling stability, and retains 89% of the initial capacity after two thousand cycles at 20 C. Moreover, the full cell using the frogspawn-inspired NaTi2(PO4)3-C as the anode and Na0.44MnO2 as the cathode is capable of ultralong cycling up to one thousand cycles at alternate 10 and 60 C, which is among the best of state-of-the-art aqueous sodium ion systems. Therefore, the frogspawn-inspired architecture provides a new strategy to the tailored design of polyanion materials for high-power applications. PMID:26490545

  16. A novel high capacity positive electrode material with tunnel-type structure for aqueous sodium-ion batteries

    DOE PAGESBeta

    Wang, Yuesheng; Mu, Linqin; Liu, Jue; Yang, Zhenzhong; Yu, Xiqian; Gu, Lin; Hu, Yong -Sheng; Li, Hong; Yang, Xiao -Qing; Chen, Liquan; et al

    2015-08-06

    In this study, aqueous sodium-ion batteries have shown desired properties of high safety characteristics and low-cost for large-scale energy storage applications such as smart grid, because of the abundant sodium resources as well as the inherently safer aqueous electrolytes. Among various Na insertion electrode materials, tunnel-type Na0.44MnO2 has been widely investigated as a positive electrode for aqueous sodium-ion batteries. However, the low achievable capacity hinders its practical applications. Here we report a novel sodium rich tunnel-type positive material with a nominal composition of Na0.66[Mn0.66Ti0.34]O2. The tunnel-type structure of Na0.44MnO2 obtained for this compound was confirmed by XRD and atomic-scale STEM/EELS.more » When cycled as positive electrode in full cells using NaTi2(PO4)3/C as negative electrode in 1M Na2SO4 aqueous electrolyte, this material shows the highest capacity of 76 mAh g-1 among the Na insertion oxides with an average operating voltage of 1.2 V at a current rate of 2C. These results demonstrate that Na0.66[Mn0.66Ti0.34]O2 is a promising positive electrode material for rechargeable aqueous sodium-ion batteries.« less

  17. SAXS Investigation on the Fractal Properties of MnO2 Semiconductor Thin Films

    NASA Astrophysics Data System (ADS)

    Skatkov, Leonid; Gomozov, Valeriy

    This paper presents the results of investigations on the morphology and porous concentration distribution in the MnO2 and also the fractal properties of porous semiconductor. The volume fractal dimension are stated to be order 2.9 which is a stipulation of a highly developed porous structure of MnO2. The present results provide experimental support to the theory developed earlier.

  18. Facile controlled synthesis of MnO2 nanostructures of novel shapes and their application in batteries.

    PubMed

    Cheng, Fangyi; Zhao, Jianzhi; Song, Wene; Li, Chunsheng; Ma, Hua; Chen, Jun; Shen, Panwen

    2006-03-01

    In this paper, MnO2 nanomaterials of different crystallographic types and crystal morphologies have been selectively synthesized via a facile hydrothermal route and electrochemically investigated as the cathode active materials of primary and rechargeable batteries. Beta-MnO2 nano/microstructures, including one-dimensional (1-D) nanowires, nanorods, and nanoneedles, as well as 2-D hexagramlike and dendritelike hierarchical forms, were obtained by simple hydrothermal decomposition of an Mn(NO3)2 solution under controlled reaction conditions. Alpha- and gamma-MnO2 nanowires and nanorods were also prepared on the basis of previous literature. The as-synthesized samples were characterized by instrumental analyses such as XRD, SEM, TEM, and HRTEM. Furthermore, the obtained 1-D alpha- and gamma-MnO2 nanostructures were found to exhibit favorable discharge performance in both primary alkaline Zn-MnO2 cells and rechargeable Li-MnO2 cells, showing their potential applications in high-energy batteries. PMID:16499364

  19. Direct visual detection of MnO2 nanosheets within seconds.

    PubMed

    He, Yi; Wang, Zeru; Long, Dengying

    2016-02-01

    The increasing application of nanomaterials will inevitably lead to their release into the environment, which may pose a threat to the environment and human health. As such, there is an urgent need to detect various nanomaterials. In the present work, we present a novel, rapid, and simple visual detection of MnO2 nanosheets in buffer solution and environmental water sample. In this assay, a redox reaction between MnO2 nanosheets and 3,3',5,5'-tetramethylbenzidine (TMB) occurred, leading to the oxidation of TMB to TMB diimine. This redox reaction generated different colors dependent on the concentration of MnO2 nanosheets, including colorless, blue, green, and yellow, which allowed semiquantitative detection of MnO2 nanosheets with the naked eye. The detection range of the visual assay was 2-15 μg/mL, and the minimum concentration of MnO2 nanosheets can be visually detected at concentrations down to 2.0 μg/mL. Moreover, the developed visual assay showed a high selectivity to MnO2 nanosheets over Mn(2+) ions, tetramethylammonium hydroxide, hydrogen peroxide, graphene oxide, and graphitic carbon nitride nanosheets. PMID:26677022

  20. Electrochemical characterization of MnO2-based composite in the presence of salt-in-water and water-in-salt electrolytes as electrode for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Gambou-Bosca, Axel; Bélanger, Daniel

    2016-09-01

    The effect of the electrolyte on the electrochemical utilization of manganese dioxide as active material for electrochemical capacitor was studied by cyclic voltammetry and electrochemical impedance spectroscopy. MnO2-based composite electrodes were characterized in salt-in-water (0.65 M K2SO4, 5 M LiNO3, 0.5 M LiNO3 and 0.5 M Ca(NO3)2) and water-in-salt (5 M LiTFSI (lithium bis-trifluoromethanesulfonimide)) electrolytes. Firstly, no effect of the cation valence on the specific capacitance was observed as similar values were measured in 0.5 M LiNO3 and 0.5 M Ca(NO3)2 aqueous solutions at both low and high scan rate, when a MnO2-based composite electrode was cycled in the pseudocapacitive potential region. Secondly, it was found that in 5 M LiTFSI, a MnO2 electrode is characterized by an extended potential stability window of about 1.4 V and exhibits a high specific capacitance of 239 F g-1 per active material mass at a scan rate of 2 mV s-1. However due to the low ionic conductivity of this solution, the rate capability is limited at high scan rate.

  1. Facile preparation of MnO2 nanorods and evaluation of their supercapacitive characteristics

    NASA Astrophysics Data System (ADS)

    Aghazadeh, Mustafa; Asadi, Maryam; Maragheh, Mohammad Ghannadi; Ganjali, Mohammad Reza; Norouzi, Parviz; Faridbod, Farnoush

    2016-02-01

    The first time pulsed base (OH-) electrogeneration to the cathodic electrodeposition of MnO2 in nitrate bath was applied and MnO2 nanorods were obtained. The deposition experiments were performed under a pulse current mode with typical on-times and off-times (ton = 10 ms and toff = 50 ms) and a peak current density of 2 mA cm-2 (Ia = 2 mA cm-2). The structural characterization with XRD and FTIR revealed that the prepared MnO2 is composed of both α and γ phases. Morphological evaluations through SEM and TEM revealed that the prepared MnO2 contains nanorods of relative uniform structures (with an average diameter of 50 nm). The electrochemical measurements through cyclic voltammetry and charge-discharge techniques revealed that the prepared MnO2 nanostructures reveal an excellent capacitive behavior with specific capacitance values of 242, 167 and 98 F g-1 under the applied current densities of 2, 5 and 10 A g-1, respectively. Also, excellent long-term cycling stabilities of 94.8%, 89.1%, and 76.5% were observed after 1000 charge-discharge cycles at the current densities of 2, 5 and 10 A g-1.

  2. Electrochemical study of a novel high performance supercapacitor based on MnO2/nitrogen-doped graphene nanocomposite

    NASA Astrophysics Data System (ADS)

    Naderi, Hamid Reza; Norouzi, Parviz; Ganjali, Mohammad Reza

    2016-03-01

    A new nanocomposite was synthesized via deposition of MnO2 on Nitrogen-doped reduced graphene (MnO2/NRGO) by sonochemical method, in which, the particles of manganese oxide were uniformly distributed on NRGO sheets. The structure and morphology of MnO2/NRGO nanocomposites are characterized by X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The electrochemical supercapacitive performance of the nanocomposite was investigated by cyclic voltammetry (CV), continuous cyclic voltammetry (CCV), galvanostatic charge/discharge, and electrochemical impedance spectroscopy (EIS) methods. The MnO2/NRGO nanocomposite shows enhanced specific capacitance of 522 F g-1 at 2 mV s-1 and its high synergistic effect was compared with MnO2/RGO. The high specific capacitance and exceptionally high cyclic stability of MnO2/NRGO attributes to the doping of nitrogen and uniform dispersion of MnO2 particles on NRGO. The CCV showed that the capacity retention for MnO2/NRGO and MnO2/RGO still maintained at 96.3% and 93% after 4000 CVs. The improved supercapacitive performance enables this nanocomposite as efficient electrode material for supercapacitor electrodes.

  3. Materials and fabrication of electrode scaffolds for deposition of MnO2 and their true performance in supercapacitors

    NASA Astrophysics Data System (ADS)

    Cao, Jianyun; Li, Xiaohong; Wang, Yaming; Walsh, Frank C.; Ouyang, Jia-Hu; Jia, Dechang; Zhou, Yu

    2015-10-01

    MnO2 is a promising electrode material for high energy supercapacitors because of its large pseudo-capacitance. However, MnO2 suffers from low electronic conductivity and poor cation diffusivity, which results in poor utilization and limited rate performance of traditional MnO2 powder electrodes, obtained by pressing a mixed paste of MnO2 powder, conductive additive and polymer binder onto metallic current collectors. Developing binder-free MnO2 electrodes by loading nanoscale MnO2 deposits on pre-fabricated device-ready electrode scaffolds is an effective way to achieve both high power and energy performance. These electrode scaffolds, with interconnected skeletons and pore structures, will not only provide mechanical support and electron collection as traditional current collectors but also fast ion transfer tunnels, leading to high MnO2 utilization and rate performance. This review covers design strategies, materials and fabrication methods for the electrode scaffolds. Rational evaluation of the true performance of these electrodes is carried out, which clarifies that some of the electrodes with as-claimed exceptional performances lack potential in practical applications due to poor mass loading of MnO2 and large dead volume of inert scaffold materials/void spaces in the electrode structure. Possible ways to meet this challenge and bring MnO2 electrodes from laboratory studies to real-world applications are considered.

  4. Rechargeable Aluminum-Ion Batteries

    SciTech Connect

    Paranthaman, Mariappan Parans; Liu, Hansan; Sun, Xiao-Guang; Dai, Sheng; Brown, Gilbert M

    2015-01-01

    This chapter reports on the development of rechargeable aluminum-ion batteries. A possible concept of rechargeable aluminum/aluminum-ion battery based on low-cost, earth-abundant Al anode, ionic liquid EMImCl:AlCl3 (1-ethyl-3-methyl imidazolium chloroaluminate) electrolytes and MnO2 cathode has been proposed. Al anode has been reported to show good reversibility in acid melts. However, due to the problems in demonstrating the reversibility in cathodes, alternate battery cathodes and battery concepts have also been presented. New ionic liquid electrolytes for reversible Al dissolution and deposition are needed in the future for replacing corrosive EMImCl:AlCl3 electrolytes.

  5. Synthesis and characterization of whisker-shaped MnO2 nanostructure at room temperature

    NASA Astrophysics Data System (ADS)

    Jaganyi, Deogratius; Altaf, Mohammad; Wekesa, Isaac

    2013-08-01

    Manganese dioxide nanoparticles have been synthesized, via a facile one-step solution phase approach, by the reduction of potassium permanganate with sodium thiosulphate at room temperature. Upon addition of thiosulphate to the solution of permanganate, a transparent dark-brown color species appeared which was stable for several months. The obtained MnO2 solution was characterized by means of UV-vis spectra, Transmission electron microscopy (TEM), and Fourier transforms infrared spectroscopy. Fourier transforms infrared spectroscopy spectra of pure MnO2 show the occurrence of O-Mn-O vibrational mode at around 600 and 475 cm-1. The chemical composition was obtained by EDX analysis and confirmed the presence of Mn and O in the sample. From the TEM image, the surface morphology of the sample shows uniformly dispersed particles, which are spherical in shape. The selected area electron diffraction patterns revealed that the MnO2 are crystalline in nature.

  6. Structural evolution of tetragonal MnO2 and its electrochemical behavior

    NASA Astrophysics Data System (ADS)

    Shafi, P. Muhammed; Bose, A. Chandra

    2016-05-01

    MnO2 nanoparticles were synthesized by simple chemical precipitation method and were subjected to different heat treatment process. The structural evolution of as-prepared MnO2 nanoparticles at different annealing temperature was confirmed by XRD analysis. The weight loss as well as the heat flow associated with the thermal decomposition was studied by thermogravimetric analysis (TGA) along with differential thermal analysis (DTA). The functional group and phase formation were confirmed by Fourier transform infrared spectroscopy (FTIR). Finally electrochemical properties were evaluated using cyclic voltammetry (CV) and galvanostatic charge-discharge techniques. The cyclic voltammogram and charge-discharge curve of 450 ˚C annealed MnO2 nanoparticles exhibited relatively good capacitive behavior.

  7. Na3Ti2(PO4)(3) as a sodium-bearing anode for rechargeable aqueous sodium-ion batteries

    SciTech Connect

    Li, Z; Ravnsbaek, DB; Xiang, K; Chiang, YM

    2014-07-01

    Na3Ti2(PO4)(3) synthesized as fine carbon-coated powders is demonstrated for the first time to be a suitable sodium-bearing anode material for rechargeable aqueous sodium-ion batteries (ANaBs). Importantly, Na3Ti2(PO4)(3) is found to be stable in deoxygenated water, enabling use of this material in aqueous systems. As a sodiated anode, it allows use of sodium-depleted cathode materials that require supply of sodium-ions from the anode. As an example, we demonstrate for the first time the use of olivine FePO4 as a cathode in an ANaB. (C) 2014 Elsevier B.V. All rights reserved.

  8. Hydrothermal synthesis and characterization of orchid-like MnO 2 nanostructures

    NASA Astrophysics Data System (ADS)

    Li, Xueliang; Li, Wenjie; Chen, Xiangying; Shi, Chengwu

    2006-12-01

    Orchid-like Cr-doped MnO 2 nanostructures have been synthesized via a hydrothermal method, using KClO 3 as the oxidant. The as-obtained samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE-SEM). Results show that the morphologies of orchid-like MnO 2 are made up of nanorods. The influences of chromium in the solution on the morphology of the products are discussed. The electrochemical characterization was carried out by cyclic voltammetry, which indicated that the products were excellent electrode material for super-capacitor.

  9. The effect of fluxing agent MnO2 on alumina silicate porcelain insulator properties

    NASA Astrophysics Data System (ADS)

    Dudi, Dharmender; Shekhawat, M. S.; Singh, G. P.

    2016-05-01

    Higher strength electrical porcelain is a requirement for industry. This will be achieved by a specific composition of raw materials, which is consisted of clays and feldspars. High mechanical resistance, low porosity and water absorption are among their important properties. By decreasing the silica and increasing the alumina provides a higher mechanical strength in porcelain but on the other hand increases the body's baking temperature. Therefore adding MnO2 in different percentage is a suitable and practical solution to improve strength without increasing sinter temperature. Results have shown that addition of 1% MnO2 in body enhances mechanical strength of the body.

  10. Neutron Scattering Studies of Magnetic Structure and Excitations in Na5/8MnO2

    NASA Astrophysics Data System (ADS)

    Chisnell, Robin; Li, Xin; Ma, Xiaohua; Su, Dong; Liu, Lei; Ong, Shyue Ping; Chen, Hailong; Toumar, Alexandra; Idrobo, Juan-Carlos; Lei, Yuechuan; Bai, Jianming; Wang, Feng; Lynn, Jeffrey; Lee, Young; Ceder, Gerbrand

    2015-03-01

    NaxTMO2 (TM=transition metal) materials consist of alternating layers of Na and TM ions with the TM ions arranged on a geometrically frustrated triangular lattice. Na can be easily and reversibly removed from these materials, making them of interest for application in rechargeable batteries and allowing for exploration of their rich phase diagrams as a function of Na concentration. Na ordering is an important factor in ground state selection, and is driven by electrostatic interactions in many NaxTMO2 systems. The series NaxMnO2 differs in that Na ordering is driven by a cooperative Jahn-Teller effect, due to the coexistence of Jahn-Teller active Mn3+ and non-active Mn4+ ions. We have recently shown the existence of a charge stripe ordering a in the material Na5/8MnO2. At low temperatures a magnetic stripe order also develops. We present neutron diffraction and inelastic scattering measurements and examine the details of the magnetic structure and excitations in the magnetic stripe ordered phase.

  11. A frogspawn-inspired hierarchical porous NaTi2(PO4)3-C array for high-rate and long-life aqueous rechargeable sodium batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Baidan; Lin, Bo; Zhang, Sen; Deng, Chao

    2015-11-01

    Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in a hierarchical porous array, which exhibits superior mechanical strength and high-efficiency oxygen permeability. It can be used as a model for designing a new high-performance electrode material, which has advantages such as a high surface area, fast mass transport and superior durability. Herein, we report a frogspawn-like NaTi2(PO4)3/C array prepared by a facile preform impregnation strategy. The framework is formed by a hollow carbon sphere connected by the NaTi2(PO4)3/C skeleton, and its hollow is filled with the NaTi2(PO4)3 nanospheres. The whole hierarchical porous three-dimensional array copies the structure of a frogspawn. This unique structure not only enables easy electrolyte percolation and fast electron/ion transport, but also enhances the reversible capacity and cycling durability. When it is applied as an anode of the aqueous sodium ion battery, it exhibits favorable high rate capability and superior cycling stability, and retains 89% of the initial capacity after two thousand cycles at 20 C. Moreover, the full cell using the frogspawn-inspired NaTi2(PO4)3-C as the anode and Na0.44MnO2 as the cathode is capable of ultralong cycling up to one thousand cycles at alternate 10 and 60 C, which is among the best of state-of-the-art aqueous sodium ion systems. Therefore, the frogspawn-inspired architecture provides a new strategy to the tailored design of polyanion materials for high-power applications.Hollow micro/nano-arrays have attracted tremendous attention in the field of energy conversion and storage, but such structures usually compromise the volumetric energy density of the electrode materials. Frogspawn consists of a spawn core and a transparent jelly shell organized in

  12. Preparation and the Electrochemical Performance of MnO2/PANI@CNT Composite for Supercapacitors.

    PubMed

    Wang, Hongjuan; Wang, Xiaohui; Peng, Cheng; Peng, Feng; Yu, Hao

    2015-01-01

    Polyaniline (PANI) was settled on the surface of CNTs in advance and then used as self-sacrifice reducing agent that would react with KMnO4 to prepare MnO2/PANI@CNT supercapacitor material. With PANI substituting for CNTs to participant the redox reaction, CNTs was protected from being destroyed and could maintain its original morphology and conductivity. The results of cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) show that the optimal capacitive performance can be reached at the MnO2 loading of 64.4 wt% and the pH of 1 during the deposition of MnO2. With the protective PANI, MnO2/PANI@CNT composite exhibits the superior specific capacitance of 215.8 F/g at a current density of 200 mA/g and remains 86.5% of its maximal specific capacitance at a current density of 1000 mA/g. PMID:26328431

  13. High Pseudocapacitive Performance of MnO2 Nanowires on Recyclable Electrodes.

    PubMed

    Han, Zhao Jun; Bo, Zheng; Seo, Dong Han; Pineda, Shafique; Wang, Ye; Yang, Hui Ying; Ostrikov, Kostya Ken

    2016-05-10

    Manganese oxides are promising pseudocapacitve materials for achieving both high power and energy densities in pseudocapacitors. However, it remains a great challenge to develop MnO2 -based high-performance electrodes due to their low electrical conductance and poor stability. Here we show that MnO2 nanowires anchored on electrochemically modified graphite foil (EMGF) have a high areal capacitance of 167 mF cm(-2) at a discharge current density of 0.2 mA cm(-2) and a high capacitance retention after 5000 charge/discharge cycles (115 %), which are among the best values reported for any MnO2 -based hybrid structures. The EMGF support can also be recycled and the newly deposited MnO2 -based hybrids retain similarly high performance. These results demonstrate the successful preparation of pseudocapacitors with high capacity and cycling stability, which may open a new opportunity towards a sustainable and environmentally friendly method of utilizing electrochemical energy storage devices. PMID:27059434

  14. Effect of Fe doping on the electrochemical capacitor behavior of MnO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Poonguzhali, R.; Shanmugam, N.; Gobi, R.; Senthilkumar, A.; Viruthagiri, G.; Kannadasan, N.

    2015-10-01

    In this work, the influence of Fe doping on the capacitance behavior of MnO2 nanoparticles synthesized by chemical precipitation was investigated. During the doping process the concentration of Fe was increased from 0.025 M to 0.125 M in steps of 0.025 M. The products obtained were characterized by X-ray diffraction, Fourier infrared spectroscopy, scanning electron microscopy and N2 adsorption-desorption isotherms. To demonstrate the suitability of Fe-doped MnO2 for capacitor applications, cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance were recorded. Among the different levels of doping, the specific capacitance of 912 F/g was delivered by 0.075 M of Fe-doped MnO2 at a scan rate of 10 mV/s, which is almost more than fourfold that of the bare MnO2 electrode (210 F/g). Moreover, for the same concentration the charge, discharge studies revealed the highest specific capacitance of 1084 F/g at a current density of 10 A/g.

  15. Constructing MnO2/single crystalline ZnO nanorod hybrids with enhanced photocatalytic and antibacterial activity

    NASA Astrophysics Data System (ADS)

    Yu, Weiwei; Liu, Tiangui; Cao, Shiyi; Wang, Chen; Chen, Chuansheng

    2016-07-01

    In order to improve the photocatalytic and antibacterial activity of ZnO nanorods, ZnO nanorods decorated with MnO2 nanoparticles (MnO2/ZnO nanorod hybrids) were prepared by using microwave assisted coprecipitation method under the influence of hydrogen peroxide, and the structure, photocatalytic activity and antibacterial property of the products were studied. Experimental results indicated that MnO2 nanoparticles are decorated on the surface of single crystalline ZnO nanorods. Moreover, the resultant MnO2/ZnO nanorod hybrids have been proven to possess good photocatalytic and antibacterial activity, which their degradated efficiency for Rhodamin B (RhB) is twice as the pure ZnO nanorods. Enhancement for photocatalytic and antibacterial activity is mainly attributed to the low band gap energy and excellent electrochemical properties of MnO2 nanoparticles.

  16. Coupled biotic-abiotic oxidation of organic matter by biogenic MnO_{2}

    NASA Astrophysics Data System (ADS)

    Gonzalez, Julia; Peña, Jasquelin

    2016-04-01

    Some reactive soil minerals are strongly implicated in stabilising organic matter. However, others can play an active role in the oxidation of organic molecules. In natural systems, layer-type manganese oxide minerals (MnO2) typically occur as biomineral assemblages consisting of mineral particles and microbial biomass. Both the mineral and biological fractions of the assemblage can be powerful oxidants of organic C. The biological compartment relies on a set of enzymes to drive oxidative transformations of reduced C-substrates, whereas MnO2 minerals are strong, less specific abiotic oxidants that are assumed to rely on interfacial interactions between C-substrates and the mineral surface. This project aims to understand the coupling between microbial C mineralization and abiotic C oxidation mediated by MnO2 in bacterial-MnO2 assemblages. Specifically, under conditions of high C turnover, microbial respiration can significantly alter local pH, dissolved oxygen and pool of available reductants, which may modify rates and mechanism of C oxidation by biotic and abiotic components. We first investigated changes in the solution chemistry of Pseudomonas putida suspensions exposed to varying concentrations of glucose, chosen to represent readily bioavailable substrates in soils. Glucose concentrations tested ranged between 0 and 5.5mM and changes in pH, dissolved oxygen and dissolved organic and inorganic carbon were tracked over 48h. We then combined literature review and wet-chemical experiments to compile the pH dependence of rates of organic substrate oxidation by MnO2, including glucose. Our results demonstrate a strong pH dependence for these abiotic reactions. In assemblages of P. putida - MnO2, kinetic limitations for abiotic C oxidation by MnO2 are overcome by changes in biogeochemical conditions that result from bacterial C metabolism. When extrapolated to a soil solution confronted to an input of fresh dissolved organic matter, bacterial C metabolism of the labile fraction may lower solution pH into a regime that favours abiotic oxidation of recalcitrant C by MnO2. This project demonstrates that the co-occurrence of mineral particles with metabolically active cells provides a direct link between the C and Mn cycles.

  17. Constructing Hierarchically Hollow Core-Shell MnO2 /C Hybrid Spheres for High-Performance Lithium Storage.

    PubMed

    Wang, Gang; Sun, Yuhan; Li, Debao; Wei, Wei; Feng, Xinliang; Müllen, Klaus

    2016-08-01

    Hierarchical MnO2 /C hybrid spheres (MCS@MnO2 ), consisting of numerous hollow core-shell MnO2 @C nanospheres, are developed via a facile deposition process. The well-defined inner voids and robust carbon framework endow MCS@MnO2 with excellent mechanical stability, efficient utilization of MnO2 , and enhanced reaction kinetics for Li-ion batteries, therefore leading to large specific capacities, superior rate capability, and long-term cycling stability. PMID:27275631

  18. MnO2 nanotube-Pt/graphene mixture as an ORR catalyst for proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Divya, P.; Ramaprabhu, S.

    2013-02-01

    In the present study, MnO2 nanotubes are synthesized by hydrothermal method and Pt/graphene by co reduction of hexachloroplatinic acid and graphite oxide. The formation of MnO2 nanotubes and Pt/graphene are confirmed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy. MnO2 nanotubes are mixed with Pt/graphene is applied as the ORR catalyst in proton exchange membrane fuel cell. The single cell measurement is carried out after fabricating the membrane electrode assembly and polarization curves are recorded at different temperatures and the results are discussed.

  19. Optimization of MnO 2/vertically aligned carbon nanotube composite for supercapacitor application

    NASA Astrophysics Data System (ADS)

    Amade, Roger; Jover, Eric; Caglar, Burak; Mutlu, Toygan; Bertran, Enric

    The optimization strategy for producing manganese oxide supercapacitors based on vertically aligned carbon nanotubes (VACNTs) deposited on large area electrodes is presented. A single sequential process of sputtering, annealing and plasma enhanced chemical vapour deposition (PECVD) is applied to produce dense and uniform VACNTs electrodes. As dielectric layer of the supercapacitor, manganese oxide is electrodeposited lining the surface of the VACNTs electrodes. The control of the growing parameters such as catalyst thickness layer, temperature and deposition time for tuning the density, length and diameter of the VACNTs and their structure are found to be key points for the optimization of the MnO 2 electrodeposition process in view to improve the efficiency of the supercapacitor devices. The electrochemical properties of the obtained electrodes are characterized using cyclic voltammetry and galvanostatic charge-discharge techniques. A specific capacitance of 642 Fg -1 is obtained for MnO 2/VACNTs nanocomposite electrode at a scan rate of 10 mV s -1.

  20. Carbon-based air electrodes carrying MnO 2 in zinc-air batteries

    NASA Astrophysics Data System (ADS)

    Wei, Zidong; Huang, Wenzhang; Zhang, Shengtao; Tan, Jun

    Catalysts prepared from the carbon black impregnated with manganous nitrate solution and then heated at temperature from 270°C to 450°C were investigated. It was found that the impregnated catalysts heated at temperature of 340°C exhibited the best catalytic activity for oxygen reduction in alkaline electrolyte. It was also found that the XRD spectra of pyrolytic MnO 2 from manganous nitrate over 340°C were different from those below 340°C. The enhanced catalysis of air electrodes was ascribed to the formation of MnO 2 crystal with d-value of 2.72 Å as the impregnated-catalysts was heated at temperature of 340°C. The other factors in preparation of air electrodes were also discussed.

  1. Giant Seebeck coefficient thermoelectric device of MnO2 powder.

    PubMed

    Song, FangFang; Wu, Liming; Liang, S

    2012-03-01

    We report a giant Seebeck coefficient (S) thermoelectric (TE) material-MnO(2) powder-and the design of a practical MnO(2) TE generator to light up a regular light emitting diode (LED). The S of MnO(2) powder was measured to be higher than 20,000 μV K(-1), which is about 100 times higher than the state-of-the-art of Bi(2)Te(3), one of the best TE materials. The giant S is very possibly closely related to the surface density of the electronic state (DOS), the Fermi energy level. The very high S and therefore high power factor is technologically important for transient TE cooling. PMID:22293218

  2. Momentum-dependent band spin splitting in semiconducting MnO2: a density functional calculation.

    PubMed

    Noda, Yusuke; Ohno, Kaoru; Nakamura, Shinichiro

    2016-05-11

    Recently, manganese-oxide compounds have attracted considerable attention, in particular, as candidate materials for photochemical water-splitting reactions. Here, we investigate electronic states of pristine manganese dioxides (MnO2) in different crystal phases using spin-polarized density functional theory (DFT) with Hubbard U correction. Geometrical structures and band dispersions of α-, β-, δ-, and λ-MnO2 crystals with collinear magnetic [ferromagnetic (FM) and antiferromagnetic (AFM)] orders are discussed in detail. We reveal that penalty energies that arise by violating the Goodenough-Kanamori rule are important and the origin of the magnetic interactions of the MnO2 crystals is governed by the superexchange interactions of Mn-O-Mn groups. In addition, it is found that momentum-dependent band spin splitting occurs in the AFM α-, β-, and δ-MnO2 crystals while no spin splitting occurs in the AFM λ-MnO2 crystal. Our results show that spin-split band dispersions stem from the different orientations of Mn-centred oxygen octahedra. Such interesting electronic states of the MnO2 crystals are unraveled by our discussion on the relationship between the effective (spin-dependent) single-electron potentials and the space-group symmetry operations that map up-spin Mn atoms onto down-spin Mn atoms. This work provides a basis to understand the relationship between the spin-dependent electronic states and the crystallography of manganese oxides. Another relationship to the recent experimental observations of the photochemical oxygen evolution of MnO2 crystals is also discussed. PMID:27119122

  3. Direct Chemical Synthesis of MnO2 Nanowhiskers on Transition-Metal Carbide Surfaces for Supercapacitor Applications.

    PubMed

    Rakhi, Raghavan Baby; Ahmed, Bilal; Anjum, Dalaver; Alshareef, Husam N

    2016-07-27

    Transition-metal carbides (MXenes) are an emerging class of two-dimensional materials with promising electrochemical energy storage performance. Herein, for the first time, by direct chemical synthesis, nanocrystalline ε-MnO2 whiskers were formed on MXene nanosheet surfaces (ε-MnO2/Ti2CTx and ε-MnO2/Ti3C2Tx) to make nanocomposite electrodes for aqueous pseudocapacitors. The ε-MnO2 nanowhiskers increase the surface area of the composite electrode and enhance the specific capacitance by nearly 3 orders of magnitude compared to that of pure MXene-based symmetric supercapacitors. Combined with enhanced pseudocapacitance, the fabricated ε-MnO2/MXene supercapacitors exhibited excellent cycling stability with ∼88% of the initial specific capacitance retained after 10000 cycles which is much higher than pure ε-MnO2-based supercapacitors (∼74%). The proposed electrode structure capitalizes on the high specific capacitance of MnO2 and the ability of MXenes to improve conductivity and cycling stability. PMID:27377125

  4. AlF3-coated LiMn2O4 as cathode material for aqueous rechargeable lithium battery with improved cycling stability

    NASA Astrophysics Data System (ADS)

    Tron, Artur; Park, Yeong Don; Mun, Junyoung

    2016-09-01

    In this study, we introduce AlF3-coated LiMn2O4 cathodes, which are cost-effective and environmentally benign, for use in the aqueous rechargeable lithium-ion battery. The homogeneous AlF3 coating on the LiMn2O4 powder is synthesized by a simple chemical deposition method. The thickness of the coating is controlled by varying the quantity of AlF3 used, in order to optimize the balance between polarization and surface stabilization. The optimized LiMn2O4, having 2 wt% coating of AlF3, exhibits a long cycle life having a capacity retention of 90% after 100 cycles, and a highly improved rate capability, when compared with the pristine LiMn2O4 material, in 1 M Li2SO4 aqueous electrolyte solution. The systematic surface analyses, comprising scanning electron microscopy, X-ray photoelectron spectroscopy, and electrochemical analyses, indicate that the AlF3 coating on the LiMn2O4 surface successfully reduces the surface deterioration of LiMn2O4 caused by side reactions between the electrolyte solution and the active material.

  5. [Preparation and Pb2 electrosorption characteristics of MnO2/CFP composite electrode].

    PubMed

    Liu, Fang-Yuan; Hu, Cheng-Zhi; Li, Yong-Feng; Liang, Qian-Wei

    2015-02-01

    The morphological structure and electrochemical properties of the electrode materials have direct impact on the electrosorption results. In this paper, Manganese dioxide ( MnO2) was composed on flexible carbon fiber paper ( CFP) via anodic electrodeposition technique to prepare the MnO2/CFP hybrid electrodes. The electrodes materials prepared showed stable electrochemical property, remarkable electrochemical capacitance, and the specific capacitance reached up to 360 F x g(-1). Electrosorption was conducted with this MnO2/CFP hybrid electrode to treat the waste water with an initial Pb2+ concentration of 6 mg x L(-1), and the effects of deposition time, initial pH, and voltage value on the electrosorption were investigated. It was shown that when the electrodeposition time was 500 s and the application of voltage value was 1.0 V, pH = 5.0, the best electroabsorption result was achieved. After 3 h electrosorption, the residual Pb2+ in the solution was lower than 0.01 mg x L(-1), and the removal efficiency could reach 99%. This study provides a new technology option for the removal of heavy metal ions in low concentrations in the waste water. PMID:26031082

  6. Quantitatively Predict the Potential of MnO2 Polymorphs as Magnesium Battery Cathodes.

    PubMed

    Ling, Chen; Zhang, Ruigang; Mizuno, Fuminori

    2016-02-01

    Despite tremendous efforts denoted to magnesium battery research, the realization of magnesium battery is still challenged by the lack of cathode candidate with high energy density, rate capability and good recyclability. This situation can be largely attributed to the failure to achieve sustainable magnesium intercalation chemistry. In current work we explored the magnesiation of distinct MnO2 polymorphs using first-principles calculations, focusing on providing quantitative analysis about the feasibility of magnesium intercalation. Consistent with experimental observations, we predicted that ramsdellite-MnO2 and α-MnO2 are conversion-type cathodes while nanosized spinel-MnO2 and MnO2 isostructual to CaFe2O4 are better candidates for Mg intercalation. Key properties that restrict Mg intercalation include not only sluggish Mg migration but also stronger distortion that damages structure integrity and undesirable conversion reaction. We demonstrate that by evaluating the reaction free energy, structural deformation associated with the insertion of magnesium, and the diffusion barriers, a quantitative evaluation about the feasibility of magnesium intercalation can be well established. Although our current work focuses on the study of MnO2 polymorphs, the same evaluation can be applied to other cathode candidates, thus paving the road to identify better cathode candidates in future. PMID:26830338

  7. Prevention of PVDF ultrafiltration membrane fouling by coating MnO2 nanoparticles with ozonation

    PubMed Central

    Yu, Wenzheng; Brown, Matthew; Graham, Nigel. J. D.

    2016-01-01

    Pre-treatment is normally required to reduce or control the fouling of ultrafiltration (UF) membranes in drinking water treatment process. Current pre-treatment methods, such as coagulation, are only partially effective to prevent long-term fouling. Since biological activities are a major contributor to accumulated fouling, the application of an oxidation/disinfection step can be an effective complement to coagulation. In this study, a novel pre-treatment method has been evaluated at laboratory scale consisting of the addition of low dose ozone into the UF membrane tank after coagulation and the use of a hollow-fibre membrane coated with/without MnO2 nanoparticles over a test period of 70 days. The results showed that there was minimal fouling of the MnO2 coated membrane (0.5 kPa for 70 days), while the uncoated membrane experienced both reversible and irreversible fouling. The difference was attributed to the greatly reduced presence of bacteria and organic matter because of the catalytic decomposition of ozone to hydroxyl radicals and increase of the hydrophilicity of the membrane surface. In particular, the MnO2 coated membrane had a much thinner cake layer, with significantly less polysaccharides and proteins, and much less accumulated organic matter within the membrane pores. PMID:27436142

  8. Prevention of PVDF ultrafiltration membrane fouling by coating MnO2 nanoparticles with ozonation.

    PubMed

    Yu, Wenzheng; Brown, Matthew; Graham, Nigel J D

    2016-01-01

    Pre-treatment is normally required to reduce or control the fouling of ultrafiltration (UF) membranes in drinking water treatment process. Current pre-treatment methods, such as coagulation, are only partially effective to prevent long-term fouling. Since biological activities are a major contributor to accumulated fouling, the application of an oxidation/disinfection step can be an effective complement to coagulation. In this study, a novel pre-treatment method has been evaluated at laboratory scale consisting of the addition of low dose ozone into the UF membrane tank after coagulation and the use of a hollow-fibre membrane coated with/without MnO2 nanoparticles over a test period of 70 days. The results showed that there was minimal fouling of the MnO2 coated membrane (0.5 kPa for 70 days), while the uncoated membrane experienced both reversible and irreversible fouling. The difference was attributed to the greatly reduced presence of bacteria and organic matter because of the catalytic decomposition of ozone to hydroxyl radicals and increase of the hydrophilicity of the membrane surface. In particular, the MnO2 coated membrane had a much thinner cake layer, with significantly less polysaccharides and proteins, and much less accumulated organic matter within the membrane pores. PMID:27436142

  9. Prevention of PVDF ultrafiltration membrane fouling by coating MnO2 nanoparticles with ozonation

    NASA Astrophysics Data System (ADS)

    Yu, Wenzheng; Brown, Matthew; Graham, Nigel. J. D.

    2016-07-01

    Pre-treatment is normally required to reduce or control the fouling of ultrafiltration (UF) membranes in drinking water treatment process. Current pre-treatment methods, such as coagulation, are only partially effective to prevent long-term fouling. Since biological activities are a major contributor to accumulated fouling, the application of an oxidation/disinfection step can be an effective complement to coagulation. In this study, a novel pre-treatment method has been evaluated at laboratory scale consisting of the addition of low dose ozone into the UF membrane tank after coagulation and the use of a hollow-fibre membrane coated with/without MnO2 nanoparticles over a test period of 70 days. The results showed that there was minimal fouling of the MnO2 coated membrane (0.5 kPa for 70 days), while the uncoated membrane experienced both reversible and irreversible fouling. The difference was attributed to the greatly reduced presence of bacteria and organic matter because of the catalytic decomposition of ozone to hydroxyl radicals and increase of the hydrophilicity of the membrane surface. In particular, the MnO2 coated membrane had a much thinner cake layer, with significantly less polysaccharides and proteins, and much less accumulated organic matter within the membrane pores.

  10. Capture and release of cancer cells using electrospun etchable MnO2 nanofibers integrated in microchannels

    NASA Astrophysics Data System (ADS)

    Liu, Hui-qin; Yu, Xiao-lei; Cai, Bo; You, Su-jian; He, Zhao-bo; Huang, Qin-qin; Rao, Lang; Li, Sha-sha; Liu, Chang; Sun, Wei-wei; Liu, Wei; Guo, Shi-shang; Zhao, Xing-zhong

    2015-03-01

    This paper introduces a cancer cell capture/release microchip based on the self-sacrificed MnO2 nanofibers. Through electrospinning, lift-off and soft-lithography procedures, MnO2 nanofibers are tactfully fabricated in microchannels to implement enrichment and release of cancer cells in liquid samples. The MnO2 nanofiber net which mimics the extra cellular matrix can lead to high capture ability with the help of a cancer cell-specific antibody bio-conjugation. Subsequently, an effective and friendly release method is carried out by using low concentration of oxalic acid to dissolve the MnO2 nanofiber substrate while keeping high viability of those released cancer cells at the same time. It is conceivable that our microchip may have potentials in realizing biomedical analysis of circulating tumor cells for biological and clinical researches in oncology.

  11. MnO2 Nanorods Intercalating Graphene Oxide/Polyaniline Ternary Composites for Robust High-Performance Supercapacitors

    PubMed Central

    Han, Guangqiang; Liu, Yun; Zhang, Lingling; Kan, Erjun; Zhang, Shaopeng; Tang, Jian; Tang, Weihua

    2014-01-01

    New ternary composites of MnO2 nanorods, polyaniline (PANI) and graphene oxide (GO) have been prepared by a two-step process. The 100 nm-long MnO2 nanorods with a diameter ~20 nm are conformably coated with PANI layers and fastened between GO layers. The MnO2 nanorods incorporated ternary composites electrode exhibits significantly increased specific capacitance than PANI/GO binary composite in supercapacitors. The ternary composite with 70% MnO2 exhibits a highest specific capacitance reaching 512 F/g and outstanding cycling performance, with ~97% capacitance retained over 5000 cycles. The ternary composite approach offers an effective solution to enhance the device performance of metal-oxide based supercapacitors for long cycling applications. PMID:24769835

  12. Synthesis of honeycomb MnO2 nanospheres/carbon nanoparticles/graphene composites as electrode materials for supercapacitors

    NASA Astrophysics Data System (ADS)

    Xiong, Yachao; Zhou, Min; Chen, Hao; Feng, Lei; Wang, Zhao; Yan, Xinzhu; Guan, Shiyou

    2015-12-01

    Improving the electrochemical performance of manganese dioxide (MnO2) electrodes is of great significance for supercapacitors. In this study, a novel honeycomb MnO2 nanospheres/carbon nanoparticles/graphene composites has been fabricated through freeze-drying method. The honeycomb MnO2 nanospheres are well inserted and dispersed on the graphene. Carbon nanoparticles in the composites act as spacers to effectively prevent graphene from restacking and agglomeration, construct efficient 3D conducting architecture with graphene for honeycomb MnO2 nanospheres, and alleviate the aggregation of honeycomb MnO2 nanospheres by separating them from each other. As a result, such honeycomb MnO2 nanospheres/carbon nanoparticles/graphene composites display much improved electrochemical capacitive performance of 255 F g-1 at a current density of 0.5 A g-1, outstanding rate capability (150 F g-1 remained at a current density of 20 A g-1) and good cycling stability (83% of the initial capacitance retained after 1000 charge/discharge cycles). The strategy for the synthesis of these composites is very effective.

  13. Reversible aqueous zinc/manganese oxide energy storage from conversion reactions

    NASA Astrophysics Data System (ADS)

    Pan, Huilin; Shao, Yuyan; Yan, Pengfei; Cheng, Yingwen; Han, Kee Sung; Nie, Zimin; Wang, Chongmin; Yang, Jihui; Li, Xiaolin; Bhattacharya, Priyanka; Mueller, Karl T.; Liu, Jun

    2016-05-01

    Rechargeable aqueous batteries such as alkaline zinc/manganese oxide batteries are highly desirable for large-scale energy storage owing to their low cost and high safety; however, cycling stability is a major issue for their applications. Here we demonstrate a highly reversible zinc/manganese oxide system in which optimal mild aqueous ZnSO4-based solution is used as the electrolyte, and nanofibres of a manganese oxide phase, α-MnO2, are used as the cathode. We show that a chemical conversion reaction mechanism between α-MnO2 and H+ is mainly responsible for the good performance of the system. This includes an operating voltage of 1.44 V, a capacity of 285 mAh g‑1 (MnO2), and capacity retention of 92% over 5,000 cycles. The Zn metal anode also shows high stability. This finding opens new opportunities for the development of low-cost, high-performance rechargeable aqueous batteries.

  14. Binder-free flexible LiMn2O4/carbon nanotube network as high power cathode for rechargeable hybrid aqueous battery

    NASA Astrophysics Data System (ADS)

    Zhu, Xiao; Wu, Xianwen; Doan, The Nam Long; Tian, Ye; Zhao, Hongbin; Chen, P.

    2016-09-01

    Highly flexible LiMn2O4/carbon nanotube (CNT) electrodes are developed and used as a high power cathode for the Rechargeable Hybrid Aqueous Battery (ReHAB). LiMn2O4 particles are entangled into CNT networks, forming a self-supported free-standing hybrid films. Such hybrid films can be used as electrodes of ARLB without using any additional binders. The binder-free LiMn2O4/CNT electrode exhibits good mechanical properties, high conductivity, and effective charge transport. High-rate capability and high cycling stability are obtained. Typically, the LiMn2O4/CNT electrode achieves a discharge capacity of 72 mAh g-1 at the large-current of 20 C (1 C = 120 mAh g-1), and exhibits good cycling performance and high reversibility: Coulombic efficiency of almost 100% over 300 charge-discharge cycles at 4 C. By reducing the weight, and improving the large-current rate capability simultaneously, the LiMn2O4/CNT electrode can highly enhance the energy/power density of ARLB and hold potential to be used in ultrathin, lightweight electronic devices.

  15. Reduced Graphene-Wrapped MnO2 Nanowires Self-Inserted with Co3 O4 Nanocages: Remarkable Enhanced Performances for Lithium-Ion Anode Applications.

    PubMed

    Zhu, Qi; Li, Yunhui; Gao, Ying; Wang, Xiao; Song, Shuyan

    2016-05-10

    A simple synthetic approach for graphene-templated nanostructured MnO2 nanowires self-inserted with Co3 O4 nanocages is proposed in this work. The Co3 O4 nanocages were penetrated in situ by MnO2 nanowires. As an anode, the as-obtained MnO2 -Co3 O4 -RGO composite exhibits remarkable enhanced performance compared with the MnO2 -RGO and Co3 O4 -RGO samples. The MnO2 -Co3 O4 -RGO electrode delivers a reversible capacity of up to 577.4 mA h g(-1) after 400 cycles at 500 mA g(-1) and the Coulombic efficiency of MnO2 -Co3 O4 -RGO is about 96 %. PMID:27071726

  16. Comparative study of MnO2 nanoparticle synthesis by marine bacterium Saccharophagus degradans and yeast Saccharomyces cerevisiae.

    PubMed

    Salunke, Bipinchandra K; Sawant, Shailesh S; Lee, Sang-Ill; Kim, Beom Soo

    2015-07-01

    Microorganisms are one of the most attractive and simple sources for the synthesis of different types of metal nanoparticles. The synthesis of manganese dioxide nanoparticles (MnO2 NPs) by microorganisms from reducing potassium permanganate was investigated for the first time in the present study. The microbial supernatants of the bacterium Saccharophagus degradans ATCC 43961 (Sde 2-40) and of the yeast Saccharomyces cerevisiae showed positive reactions to the synthesis of MnO2 NPs by displaying a change of color in the permanganate solution from purple to yellow. KMnO4-specific peaks also disappeared and MnO2-specific peaks emerged at an absorption maximum of 365 nm in UV-visible spectrophotometry. The washed Sde 2-40 cells did not show any ability to synthesize MnO2 NPs. The medium and medium constituents of Sde 2-40 showed similar positive reactions as supernatants, which indicate the role of the Sde 2-40 medium constituents in the synthesis of MnO2 NPs. This suggests that microorganisms without nanoparticle synthesis ability can be misreported for their abilities to synthesize nanoparticles. S. cerevisiae washed cells showed an ability to synthesize MnO2 NPs. The strategies of keeping yeast cells in tea bags and dialysis membranes showed positive tests for the synthesis of MnO2 NPs. A Fourier transform-infrared spectroscopy study suggested roles for the proteins, alcoholic compounds, and cell walls of S. cerevisiae cells in the synthesis of MnO2 NPs. Electron-dispersive X-ray spectroscopy analyses confirmed the presence of Mn and O in the sample. X-ray photoelectron spectroscopy revealed characteristic binding energies for MnO2 NPs. Transmission electron microscopy micrographs revealed the presence of uniformly dispersed hexagonal- and spherical-shaped particles with an average size of 34.4 nm. The synthesis approach using yeast is possible by a simple reaction at low temperature without any need for catalysts, templates, or expensive and precise equipment. Therefore, this study will be useful for the easy, cost-effective, reliable, and eco-friendly production of nanomaterials. PMID:25846336

  17. Hierarchical MnO2 nanowire/graphene hybrid fibers with excellent electrochemical performance for flexible solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Ma, Wujun; Chen, Shaohua; Yang, Shengyuan; Chen, Wenping; Cheng, Yanhua; Guo, Yiwei; Peng, Shengjie; Ramakrishna, Seeram; Zhu, Meifang

    2016-02-01

    Towards rapid development of lightweight, flexible, and even wearable electronics, a highly efficient energy-storage device is required for their energy supply management. Graphene fiber-based supercapacitor is considered as one of the promising candidates because of the remarkable mechanical and electrical properties of graphene fibers. However, supercapacitors based on bare graphene fibers generally suffer a low capacitance, which certainly restricts their potentially wide applications. In this work, hierarchically structured MnO2 nanowire/graphene hybrid fibers are fabricated through a simple, scalable wet-spinning method. The hybrid fibers form mesoporous structure with large specific surface area of 139.9 m2 g-1. The mass loading of MnO2 can be as high as 40 wt%. Due to the synergistic effect between MnO2 nanowires and graphene, the main pseudocapacitance of MnO2 and the electric double-layer capacitance of graphene are improved simultaneously. In view of the practical demonstration, a highly flexible solid-state supercapacitor is fabricated by twisting of two MnO2/graphene fibers coated by polyvinyl alcohol/H3PO4 electrolyte. The supercapacitor exhibits a high volumetric capacitance (66.1 F cm-3, normalized by the total volume of two fiber electrodes), excellent cycling stability (96% capacitance retention over 10,000 cycles), high energy and power density (5.8 mWh cm-3 and 0.51 W cm-3, respectively).

  18. Hierarchical MnO2/SnO2 heterostructures for a novel free-standing ternary thermite membrane.

    PubMed

    Yang, Yong; Zhang, Zhi-Cheng; Wang, Peng-Peng; Zhang, Jing-Chao; Nosheen, Farhat; Zhuang, Jing; Wang, Xun

    2013-08-19

    We report the synthesis of a novel hierarchical MnO2/SnO2 heterostructures via a hydrothermal method. Secondary SnO2 nanostructure grows epitaxially on the surface of MnO2 backbones without any surfactant, which relies on the minimization of surface energy and interfacial lattice mismatch. Detailed investigations reveal that the cover density and morphology of the SnO2 nanostructure can be tailored by changing the experimental parameter. Moreover, we demonstrate a bottom-up method to produce energetic nanocomposites by assembling nanoaluminum (n-Al) and MnO2/SnO2 hierarchical nanostructures into a free-standing MnO2/SnO2/n-Al ternary thermite membrane. This assembled approach can significantly reduce diffusion distances and increase their intimacy between the components. Different thermite mixtures were investigated to evaluate the corresponding activation energies using DSC techniques. The energy performance of the ternary thermite membrane can be manipulated through different components of the MnO2/SnO2 heterostructures. Overall, our work may open a new route for new energetic materials. PMID:23905515

  19. Aluminum manganese oxides with mixed crystal structure: high-energy-density cathodes for rechargeable sodium batteries.

    PubMed

    Han, Dong-Wook; Ku, Jun-Hwan; Kim, Ryoung-Hee; Yun, Dong-Jin; Lee, Seok-Soo; Doo, Seok-Gwang

    2014-07-01

    We report a new discovery for enhancing the energy density of manganese oxide (Nax MnO2 ) cathode materials for sodium rechargeable batteries by incorporation of aluminum. The Al incorporation results in NaAl(0.1) Mn(0.9) O2 with a mixture of tunnel and layered crystal structures. NaAl(0.1) Mn(0.9) O2 shows a much higher initial discharge capacity and superior cycling performance compared to pristine Na(0.65) MnO2 . We ascribe this enhancement in performance to the formation of a new orthorhombic layered NaMnO2 phase merged with a small amount of tunnel Na(0.44) MnO2 phase in NaAl(0.1) Mn(0.9) O2 , and to improvements in the surface stability of the NaAl(0.1) Mn(0.9) O2 particles caused by the formation of Al-O bonds on their surfaces. Our findings regarding the phase transformation and structure stabilization induced by incorporation of aluminum, closely related to the structural analogy between orthorhombic Na(0.44) MnO2 and NaAl(0.1) Mn(0.9) O2 , suggest a strategy for achieving sodium rechargeable batteries with high energy density and stability. PMID:24797956

  20. Inflating Strategy To Form Ultrathin Hollow MnO2 Nanoballoons.

    PubMed

    Shang, Juanjuan; Xie, Beibei; Li, Ya; Wei, Xin; Du, Na; Li, Haiping; Hou, Wanguo; Zhang, Renjie

    2016-06-28

    Ultrathin MnO2 hollow nanoballoons (UMHNBs) have a large ratio of interfacial to total atoms, corresponding to expected improved performance. However, their synthesis is a challenge due to difficulty in controlling the concentration of the unit cells. Herein, we describe a strategy to synthesize dry intact UMHNBs through a one-step synthesis by inflating MnO2 (reduced from KMnO4) with CO2 (oxidized from single-layer graphene oxide nanosheets) followed by instant freeze-drying. UMHNBs are 30-500 nm in diameter with a shell thickness of 3.7 nm, packing with laminar [MnO6] unit cells in the form of δ-MnO2. UMHNBs show efficient catalytic activity for decomposing the organic dye methylene blue (MB), 15 times the biggest reported value, and have long-term catalytic efficacy and durability. The described strategy in this paper makes use of graphene nanosheets to assemble durable ultrathin hollow nanoballoons. PMID:27187574

  1. Synthesis and electrochemical performance of polyaniline @MnO2/graphene ternary composites for electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Pan, Chao; Gu, Haiteng; Dong, Li

    2016-01-01

    We introduce a facile method to construct new ternary hierarchical nanocomposites by combining MnO2 coated one dimensional (1D) conducting polyaniline (PANI) nanowires with 2D graphene sheets (GNs). The hierarchical nanocomposite structures of PANI@MnO2/GNs (PMGNs) are further proved by X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The electrochemical characteristics of the electrodes made of the hierarchical structured PMGNs materials are determined by the CV and galvanostatic measurements. These electrochemical tests indicate that electrodes made of the nanostructured PMGNs exhibit an improved reversible capacitance of 695 F g-1 after 1000 cycles at a high current density of 4 A g-1. The ternary composites possess higher electrochemical capacitance than each individual component as supercapacitor electrode materials. Such intriguing electrochemical performance is mainly attributed to the synergistic effects of MnO2, PANI and graphene. The hierarchical ternary nanocomposites show excellent electrochemical properties for energy storage applications, which evidence their potential application as supercapacitors.

  2. Electrochemical and in situ X-ray spectroscopic studies of MnO2/reduced graphene oxide nanocomposites as a supercapacitor.

    PubMed

    Chang, Han-Wei; Lu, Ying-Rui; Chen, Jeng-Lung; Chen, Chi-Liang; Lee, Jyh-Fu; Chen, Jin-Ming; Tsai, Yu-Chen; Yeh, Ping-Hung; Chou, Wu Ching; Dong, Chung-Li

    2016-07-28

    Electrochemical and in situ X-ray absorption spectroscopy (XAS) measurements of various MnO2-coated carbon materials (MnO2/acid-functionalized carbon nanotubes (C-CNT), MnO2/reduced graphene oxide (RGO), and MnO2/RGO-Au electrodes) were conducted to evaluate the supercapacitive performances and electronic structures. MnO2 was deposited on the surface of C-CNT, RGO, and RGO-Au via a spontaneous redox reaction to facilitate the growth of the bulk form of MnO2/C-CNT and the surface forms of MnO2/RGO-based materials. Various forms of MnO2 on the carbon materials exhibited different charge/discharge behaviors. The specific capacitances of the MnO2/RGO and MnO2/RGO-Au electrodes at a current density of 1 A g(-1) were about 433 and 469 F g(-1), respectively; these values are about 1.5 times that of the MnO2/C-CNT (259 F g(-1)) electrode. Specific capacitances of 220 and 281 F g(-1) with retention rates of about 50-60% were obtained from MnO2/RGO and MnO2/RGO-Au, respectively, even at a high current density of 80 A g(-1). Experimental results revealed that the long-term electrochemical stability of the MnO2/RGO-based electrodes (with ∼90% retention) exceeded that of the MnO2/C-CNT electrode (with ∼60% retention) after 1000 cycles at a high scan rate of 80 A g(-1). This finding indicates that MnO2/RGO-based electrodes feature excellent cycling stability and rate capacity retention performance. To elucidate the atomic/electronic structures of the MnO2/C-CNT, MnO2/RGO, and MnO2/RGO-Au electrodes during the charge/discharge process, in situ XAS of the Mn K-edge was performed. The MnO2/RGO-based electrodes exhibited the least variations in the pre-peak intensity of the Mn K-edge during the charge/discharge process because a nano-network of MnO2 is homogeneously decorated on the outer surfaces of RGO-based electrodes to facilitate the growth of surface forms of MnO2/RGO and MnO2/RGO-Au. Analytical results further revealed suppression of changes in tunnel size and promotion of insertion/extraction behavior. This work, particularly the combination of cyclic voltammetry with in situ XAS measurements, will be of general value in the fields of nanomaterials and nanotechnology, and in their use in energy storage. PMID:27122222

  3. Controlled synthesis and electromagnetic performance of hollow microstructures assembled of tetragonal MnO2 nano-columns

    NASA Astrophysics Data System (ADS)

    Duan, Yuping; Jing, Hui; Liu, Zhuo; Li, Shuqing; Ma, Guojia

    2012-04-01

    Hollow microstructures assembled of tetragonal MnO2 nano-columns have been synthesized through a facile hydrothermal method with the introduction of iron ions. The obtained samples were characterized by XRD, SEM, and vector network analysis. Results reveal that the presence of Fe3+ ions leads to transformation of phase structure from α-MnO2 to a mixture of ɛ-MnO2 and α-MnO2, and it is essential to include Fe3+ ions for the formation of the hollow MnO2 microstructures. The formation mechanism was investigated and proposed in detail. Fe-doped MnO2 exhibits decreased dielectric loss, but increased magnetic loss compared with the pure one.

  4. Turning conductive carbon nanospheres into nanosheets for high-performance supercapacitors of MnO2 nanorods.

    PubMed

    Phattharasupakun, Nutthaphon; Wutthiprom, Juthaporn; Chiochan, Poramane; Suktha, Phansiri; Suksomboon, Montakan; Kalasina, Saran; Sawangphruk, Montree

    2016-02-11

    Oxidized carbon nanosheets (OCNs), produced from black carbon nanospheres and used as a conductive additive in the supercapacitor electrodes of MnO2 nanorods, can significantly improve the charge-storage performance of the symmetric MnO2-nanorod supercapacitors with a maximum specific energy of 64 W h kg(-1) and power of 3870 W kg(-1). An optimum material composition of the supercapacitor electrode finely tuned is 60 : 30 : 10 wt% of MnO2 : OCN : PVDF, respectively. Interestingly, after 5000 charge/discharge cycles, the oxidation numbers of Mn at the positive and negative electrodes of the as-fabricated supercapacitor are +3.22 and +3.04, respectively. PMID:26750504

  5. Simultaneous recovery of Zn and MnO2 from used batteries, as raw materials, by electrolysis.

    PubMed

    Buzatu, Mihai; Săceanu, Simona; Ghica, Valeriu Gabriel; Iacob, Gheorghe; Buzatu, Traian

    2013-08-01

    High purity electrolytic manganese dioxide (EMD) is the main raw material used for manufacturing of zinc and manganese based portable batteries (alkaline with manganese AlMn and zinc carbon Zn-C). Lately, due to the progressive depletion of MnO(2) natural resources, the quantity of artificially electrolytic produced MnO(2) has started to increase to satisfy the demand. This paper describes an electrolytic process for the simultaneous production of the following components:The electrolysis process was conducted in a specialized laboratory facility. The study was particularly focused on the following electrolysis process parameters: PMID:23731699

  6. Advanced Small Rechargeable Batteries

    NASA Technical Reports Server (NTRS)

    Halpert, Gerald

    1989-01-01

    Lithium-based units offer highest performance. Paper reviews status of advanced, small rechargeable batteries. Covers aqueous systems including lead/lead dioxide, cadmium/nickel oxide, hydrogen/nickel oxide, and zinc/nickel oxide, as well as nonaqueous systems. All based on lithium anodes, nonaqueous systems include solid-cathode cells (lithium/molybdenum disulfide, lithium/titanium disulfide, and lithium/vanadium oxide); liquid-cathode cells (lithium/sulfur dioxide cells); and new category, lithium/polymer cells.

  7. Nanostructured porous RuO2/MnO2 as a highly efficient catalyst for high-rate Li-O2 batteries

    NASA Astrophysics Data System (ADS)

    Wang, Guoqing; Huang, Liliang; Huang, Wei; Xie, Jian; Du, Gaohui; Zhang, Shichao; Zhu, Peiyi; Cao, Gaoshao; Zhao, Xinbing

    2015-12-01

    work. It was found that with the catalytic effect of RuO2, Li2O2 can crystallize into a thin-sheet form and realize a conformal growth on sheet-like δ-MnO2 at a current density up to 3200 mA g-1, constructing a sheet-on-sheet structure. This crystallization behavior of Li2O2 not only defers the electrode passivation upon discharge but also renders easy decomposition of Li2O2 upon charge, leading to low polarizations and reduced side reactions. This work provides a unique design of catalytic cathodes capable of controlling Li2O2 growth and sheds light on the design of high-rate, long-life Li-O2 batteries with potential applications in electric vehicles. Electronic supplementary information (ESI) available: SEM, XPS and XRD of the pristine electrodes, SAED and XPS of the discharge and charge electrodes, SEM images of the discharged electrodes with LiI, SEM images of the electrodes after recharge, voltage profiles of the Li-O2 battery with the graphene catalyst, voltage profiles of the Li-O2 battery with the RuO2/G catalyst and the SEM image of the discharged electrodes, and voltage profiles of Li-MnO2/G and Li-RuO2/G batteries tested in pure Ar. See DOI: 10.1039/c5nr07486j

  8. MnO 2-Pt/C composite electrodes for preventing voltage reversal effects with polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Wei, Z. D.; Ji, M. B.; Hong, Y.; Sun, C. X.; Chan, S. H.; Shen, P. K.

    Water is produced at the cathode of proton-exchange membrane fuel cells (PEMFC). If water were not being removed effectively, it would accumulate at the cathode of PEMFC causing the electrode flooding. The consequence is oxygen starvation, thus increasing the concentration overpotential of the cathode. In the worst scenarios, a proton (H +) reduction reaction (PRR), instead of the oxygen reduction reaction (ORR), might occur at the cathode. Not only will this cause a cathode potential drop, but the output voltage of a single cell would likely be reversed due to oxygen starvation. This phenomenon is termed the voltage reversal effect (VRE) in this paper. To study and resolve the VRE problem, a MnO 2-Pt/C composite electrode was used to replace the conventional Pt/C electrode. The authors suggest that the electrochemical reduction of MnO 2 in the composite electrode has almost the same Nernstian potential as the ORR, which would serve as a substitute for the ORR in the case of oxygen starvation. Thus, the voltage reversal effect caused by the PRR could be avoided. Two environments, N 2- and O 2-saturated H 2SO 4, were adopted to simulate two cases, i.e., O 2 starvation and O 2 rich. It was found that MnO 2-Pt/C can prevent the voltage reversal effect to a certain extent. In a N 2-saturated 1 M H 2SO 4 solution, the current density of the Pt/C electrode made of 0.6 mg Pt cm -2 was close to 0, while for the MnO 2-Pt/C composite electrode made of 0.4 mg Pt cm -2 and 0.8 mg MnO 2 cm -2, it was as high as 10 mA cm -2. Though the current generated on the MnO 2-Pt/C composite electrode in the case of oxygen starvation is not as great as that in the case when oxygen rich, it might be high enough for some cases, such as powering a radio, hearing-aid and so like miniature devices. In an O 2-saturated 1 M H 2SO 4, the presence of MnO 2 in a MnO 2-Pt/C composite electrode primarily plays a catalytic role in the ORR. It enhances the catalytic behavior of Pt for the ORR. The impedance spectra of MnO 2-Pt/C and Pt/C electrodes were carried out for the two gases in bubbled electrolyte, which further confirmed that MnO 2 in the composite electrode does substitute for oxygen as an electron-acceptor in the case of oxygen starvation. The discharged MnO 2 can then be restored to its initial state, regardless of whether it is in oxygen rich or starved conditions.

  9. MnO2-Based Electrochemical Supercapacitors on Flexible Carbon Substrates

    NASA Astrophysics Data System (ADS)

    Tadjer, Marko J.; Mastro, Michael A.; Rojo, José M.; Mojena, Alberto Boscá; Calle, Fernando; Kub, Francis J.; Eddy, Charles R.

    2014-04-01

    Manganese dioxide films were grown on large area flexible carbon aerogel substrates. Characterization by x-ray diffraction confirmed α-MnO2 growth. Three types of films were compared as a function of hexamethylenetetramine (HMTA) concentration during growth. The highest concentration of HM TA produced MnO2 flower-like films, as observed by scanning electron microscopy, whose thickness and surface coverage lead to both a higher specific capacitance and higher series resistance. Specific capacitance was measured to be 64 F/g using a galvanostatic setup, compared to the 47 F/g-specific capacitance of the carbon aerogel substrate. Such supercapacitor devices can be fabricated on large area sheets of carbon aerogel to achieve high total capacitance.

  10. A nanoporous metal recuperated MnO2 anode for lithium ion batteries.

    PubMed

    Guo, Xianwei; Han, Jiuhui; Zhang, Ling; Liu, Pan; Hirata, Akihiko; Chen, Luyang; Fujita, Takeshi; Chen, Mingwei

    2015-10-01

    Lithium-ion batteries (LIBs) have been intensively studied to meet the increased demands for the high energy density of portable electronics and electric vehicles. The low specific capacity of the conventional graphite based anodes is one of the key factors that limit the capacity of LIBs. Transition metal oxides, such as NiO, MnO2 and Fe3O4, are known to be promising anode materials that are expected to improve the specific capacities of LIBs for several times. However, the poor electrical conductivity of these oxides significantly restricts the lithium ion storage and charge/discharge rate. Here we report that dealloyed nanoporous metals can realize the intrinsic lithium storage performance of the oxides by forming oxide/metal composites. Without any organic binder, conductive additive and additional current collector, the hybrid electrodes can be directly used as anodes and show highly reversible specific capacity with high-rate capability and long cyclic stability. PMID:26350685

  11. RuO2/MnO2 composite materials for high-performance supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Jianming, Lei; Xiaomei, Chen

    2015-08-01

    Ruthenium oxide and manganese oxide nanomaterials were respectively prepared by a sol-gel process and hydrothermal synthesis method. The morphologies and microstructures of the composite nanomaterials were characterized by SEM and XRD. Based on the cyclic voltammetry, electrochemical impedance spectroscopy and constant current charge-discharge techniques, the performances of the electrodes were investigated. The results show that the composite of manganese oxide and ruthenium oxide is beneficial to improve the impedance characteristic. The electrode with 60% (mass ratio) manganese oxide has a high specific capacitance of 438 F/g and a lower inner resistance of 0.304 Ω using 38% (mass ratio) H2SO4 solution. The capacitance retention of RuO2/MnO2 composite electrode was 92.5% after 300 cycles.

  12. Recovery of MnO2 from a spent alkaline battery leach solution via ozone treatment

    NASA Astrophysics Data System (ADS)

    Cruz-Díaz, Martín R.; Arauz-Torres, Yennifer; Caballero, Francisco; Lapidus, Gretchen T.; González, Ignacio

    2015-01-01

    This work investigates the reaction rate of Mn(II) to generate solid manganese dioxide (MnO2) as a function of the gaseous ozone mass flow rate (27.5-77 g h-1). The experimental studies were carried out in a semi-continuous reactor, using a synthetic solution (300 mL of 1 M H2SO4 with 6000 ppm of Mn(II) added as MnSO4) that simulated the composition of an acid leaching solution from spent alkaline battery material (SBM). It was observed that at 1.3-1.45 V/SHE and pH < 1.0 a selective formation of MnO2 powder was obtained; at values greater than 1.45 V/SHE, permanganate ion (MnO41-) was formed. On the other hand, a linear relation was perceived between the volumetric mass transfer coefficient (kLa) and the ozone mass flow rate (19.3-77 g h-1 in 600 mL of the 1 M H2SO4 solution). The rate constant (k) was determined in the presence and absence of nonporous plastic spheres (D = 3 mm). In both cases the rate of Mn(II) conversion increased proportionally with the ozone mass flow rate, although the conversions obtained with non-porous plastic spheres (x = 82%) were always higher than those without non-porous plastic spheres (x = 72%). A pseudo-homogenous mass transfer model adequately approximated the experimental data.

  13. Hollow Carbon Nanofibers Filled with MnO2 Nanosheets as Efficient Sulfur Hosts for Lithium-Sulfur Batteries.

    PubMed

    Li, Zhen; Zhang, Jintao; Lou, Xiong Wen David

    2015-10-26

    Lithium-sulfur batteries have been investigated as promising electrochemical-energy storage systems owing to their high theoretical energy density. Sulfur-based cathodes must not only be highly conductive to enhance the utilization of sulfur, but also effectively confine polysulfides to mitigate their dissolution. A new physical and chemical entrapment strategy is based on a highly efficient sulfur host, namely hollow carbon nanofibers (HCFs) filled with MnO2 nanosheets. Benefiting from both the HCFs and birnessite-type MnO2 nanosheets, the MnO2 @HCF hybrid host not only facilitates electron and ion transfer during the redox reactions, but also efficiently prevents polysulfide dissolution. With a high sulfur content of 71 wt % in the composite and an areal sulfur mass loading of 3.5 mg cm(-2) in the electrode, the MnO2 @HCF/S electrode delivered a specific capacity of 1161 mAh g(-1) (4.1 mAh cm(-2) ) at 0.05 C and maintained a stable cycling performance at 0.5 C over 300 cycles. PMID:26349817

  14. Electrochemical preparation of MnO2 nanobelts through pulse base-electrogeneration and evaluation of their electrochemical performance

    NASA Astrophysics Data System (ADS)

    Aghazadeh, Mustafa; Maragheh, Mohammad Ghannadi; Ganjali, Mohammad Reza; Norouzi, Parviz; Faridbod, Farnoush

    2016-02-01

    Cathodic electrodeposition of MnO2 from a nitrate solution, via pulsed base (OH-) electrogeneration was performed for the first time. The deposition experiments were performed in a pulse current mode in typical on-times and off-times (i.e. ton = 1 s and toff = 1 s) with a peak current density of 2 mA cm-2 (Ia = 2 mA cm-2). The structural characterizations conducted by XRD and FTIR techniques revealed that the prepared MnO2 is composed of both α and γ phases. Morphological observation by SEM and TEM showed that the prepared MnO2 is made up of nanobelts with uniform shapes (an average diameter and length of 50 nm and 1 μm, respectively). Further electrochemical measurements by cyclic voltammetry and charge-discharge techniques revealed that the prepared MnO2 nanostructures have excellent capacitive behaviors, like a specific capacitance of 235.5 F g-1 and capacity retention of 91.3% after 1000 cycling at the scan rate of 25 mV s-1.

  15. MnO2-Carbon nanotube composite for high-areal-density supercapacitors with high rate performance

    NASA Astrophysics Data System (ADS)

    Wang, Ke; Gao, Shan; Du, Zhaolong; Yuan, Anbao; Lu, Wei; Chen, Liwei

    2016-02-01

    Practical supercapacitor devices require high areal capacitance and areal power density, and thus demand high utilization of active material and good rate performance under high areal mass loading. However, ion transport in high-mass-loading electrodes can be a challenge, which leads to deteriorate specific capacitance and rate performance. In this paper, a well-dispersed porous MnO2-carbon nanotube (CNT) composite was prepared for use as a supercapacitor electrode material. The small MnO2 nanoparticles and porous CNT network facilitated fast electron/ion transfer kinetics in the electrode. With a mass loading as high as 6.4 mg cm-2 on the electrode, the MnO2-CNT composite exhibited an excellent areal capacitance of 1.0 F cm-2 at 0.2 A g-1 (1.28 mA cm-2), with a retention of 77% even at a high current density of 20 A g-1 (128 mA cm-2). The electrode exhibited a high power density of 45.2 kW kg-1 (0.29 W cm-2) while maintaining a reasonable energy density of 16.7 Wh kg-1 (106 μWh cm-2). No apparent fading was observed even after 3000 charge/discharge cycles at 1 A g-1. This porous and evenly distributed MnO2-CNT composite has great potential for practical applications in supercapacitors.

  16. Electrode performance of romanechite for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Tsuda, Masayuki; Arai, Hajime; Nemoto, Yasue; Sakurai, Yoji

    We studied romanechite, (2×3) tunnel type manganese dioxide, as a positive electrode material for rechargeable lithium batteries. We synthesized the sample by soft chemical techniques, and its chemical composition was Ba 0.18MnO 2.10·0.42H 2O. We obtained a first discharge capacity of 120 mAh g -1 (energy density 264 mWh g -1). The capacity decreased with cycling. We examined the thermal behavior of this material, revealing its high thermal stability.

  17. A nanoporous metal recuperated MnO2 anode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Guo, Xianwei; Han, Jiuhui; Zhang, Ling; Liu, Pan; Hirata, Akihiko; Chen, Luyang; Fujita, Takeshi; Chen, Mingwei

    2015-09-01

    Lithium-ion batteries (LIBs) have been intensively studied to meet the increased demands for the high energy density of portable electronics and electric vehicles. The low specific capacity of the conventional graphite based anodes is one of the key factors that limit the capacity of LIBs. Transition metal oxides, such as NiO, MnO2 and Fe3O4, are known to be promising anode materials that are expected to improve the specific capacities of LIBs for several times. However, the poor electrical conductivity of these oxides significantly restricts the lithium ion storage and charge/discharge rate. Here we report that dealloyed nanoporous metals can realize the intrinsic lithium storage performance of the oxides by forming oxide/metal composites. Without any organic binder, conductive additive and additional current collector, the hybrid electrodes can be directly used as anodes and show highly reversible specific capacity with high-rate capability and long cyclic stability.Lithium-ion batteries (LIBs) have been intensively studied to meet the increased demands for the high energy density of portable electronics and electric vehicles. The low specific capacity of the conventional graphite based anodes is one of the key factors that limit the capacity of LIBs. Transition metal oxides, such as NiO, MnO2 and Fe3O4, are known to be promising anode materials that are expected to improve the specific capacities of LIBs for several times. However, the poor electrical conductivity of these oxides significantly restricts the lithium ion storage and charge/discharge rate. Here we report that dealloyed nanoporous metals can realize the intrinsic lithium storage performance of the oxides by forming oxide/metal composites. Without any organic binder, conductive additive and additional current collector, the hybrid electrodes can be directly used as anodes and show highly reversible specific capacity with high-rate capability and long cyclic stability. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05011a

  18. MnO2@KCu7S4 NWs hybrid compositions for high-power all-solid-state supercapacitor

    NASA Astrophysics Data System (ADS)

    Dai, Shuge; Xi, Yi; Hu, Chenguo; Yue, Xule; Cheng, Lu; Wang, Guo

    2015-01-01

    Here we present a high-power all-solid-state supercapacitor based on a novel structure of MnO2@KCu7S4 NWs. The electrodes exhibit excellent electrochemical performance with large specific capacitance of 533 F g-1 and the maximum power density 2.02 kW kg-1, still hold 85% of the capacitance over 6000 cycles. Besides, we also explored the effect of temperature on the capacitance. When compared with capacitance at different temperatures, the specific capacity at 80 °C demonstrates significantly higher. Moreover, two supercapacitors in series can power 41 light-emitting diodes (LEDs) about 4 min. These results suggest that such MnO2@KCu7S4 hybrid composite is promising for next generation high-performance supercapacitors.

  19. Capture and release of cancer cells based on sacrificeable transparent MnO2 nanospheres thin film.

    PubMed

    Huang, Qinqin; Chen, Bolei; He, Rongxiang; He, Zhaobo; Cai, Bo; Xu, Junhua; Qian, Weiyi; Chan, Helen Laiwa; Liu, Wei; Guo, Shishang; Zhao, Xing-Zhong; Yuan, Jikang

    2014-09-01

    A CTCs detection assay using transparent MnO2 nanospheres thin films to capture and release of CTCs is reported. The enhanced local topography interaction between extracellular matrix scaffolds and the antibody-coated substrate leads to improved capture efficiency. CTCs captured from artificial blood sample can be cultured and released, represent a new functional material capable of CTCs isolation and culture for subsequent studies. PMID:24652776

  20. Electrodeposited Manganese Oxides on Three-Dimensional Carbon Nanotube Substrate: Supercapacitive Behaviour in Aqueous and Organic Electrolytes

    SciTech Connect

    Nam,K.W.; Yang,X.

    2009-03-01

    Thin amorphous manganese oxide layers with a thickness of 3-5nm are electrodeposited on a carbon nanotube (CNT) film substrate that has a three-dimensional nanoporous structure (denoted asMnO2/CNT electrode). For the purpose of comparison, manganese oxide films are also electrodeposited on a flat Pt-coated Si wafer substrate (denoted as MnO2 film electrode). The pseudocapacitive properties of the MnO2 film and MnO2/CNT electrodes are examined in both aqueous electrolyte (1.0M KCl) and nonaqueousorganic electrolyte (1.0M LiClO4 in propylene carbonate). While both types of electrode showpseudocapacitive behaviour in the aqueous electrolyte, only the MnO2/CNT electrode does so in the organic electrolyte, due to its high oxide/electrolyte interfacial area and improved electron conduction through the CNT substrate. Compared with the MnO2 film electrode, the MnO2/CNT electrode shows a much higher specific capacitance and better high-rate capability, regardless of the electrolyte used.Use of the organic electrolyte results in a ∼6 times higher specific energy compared with that obtained with the aqueous electrolyte, while maintaining a similar specific power. The construction of a threedimensional nanoporous network structure consisting of a thin oxide layer on a CNT film substrate at the nm scale and the use of an organic electrolyte are promising approaches to improving the specific energyof supercapacitors.

  1. Flower-, wire-, and sheet-like MnO2-deposited diatomites: Highly efficient absorbents for the removal of Cr(VI).

    PubMed

    Du, Yucheng; Wang, Liping; Wang, Jinshu; Zheng, Guangwei; Wu, Junshu; Dai, Hongxing

    2015-03-01

    Flower-, wire-, and sheet-like MnO2-deposited diatomites have been prepared using a hydrothermal method with Mn(Ac)2, KMnO4 and/or MnSO4 as Mn source and diatomite as support. Physical properties of the materials were characterized by means of numerous analytical techniques, and their behaviors in the adsorption of chromium(VI) were evaluated. It is shown that the MnO2-deposited diatomite samples with different morphologies possessed high surface areas and abundant surface hydroxyl groups (especially the wire-like MnO2/diatomite sample). The wire-like MnO2/diatomite sample showed the best performance in the removal of Cr(VI), giving the maximum Cr(VI) adsorption capacity of 101 mg/g. PMID:25766015

  2. Morphology-controlled MnO2-graphene oxide-diatomaceous earth 3-dimensional (3D) composites for high-performance supercapacitors.

    PubMed

    Wen, Zhong Quan; Li, Min; Li, Fei; Zhu, Shi Jin; Liu, Xiao Ying; Zhang, Yu Xin; Kumeria, Tushar; Losic, Dusan; Gao, Yang; Zhang, Wei; He, Shi Xuan

    2016-01-21

    3-Dimensional (3D) composites based on a unique combination of MnO2-nanostructures, graphene oxide nanosheets and porous Diatomaceous Earth (DE) microparticles (GO-DE@MnO2) were synthesized and explored for application in high-performance supercapacitors. To explore the influence of the structural properties of MnO2 nanostructures on supercapacitor performances, several MnO2 structures with nanosheet and nanowire morphologies were synthesized and characterized. The prepared GO-DE@MnO2 composites with MnO2 nanosheets due to their higher conductivity and higher surface area showed a larger specific capacitance of 152.5 F g(-1) and a relatively better cycle stability (83.3% capacitance retention after 2000 cycles at a scan rate of 2 A g(-1)), indicating great potential for application in supercapacitors. PMID:26645931

  3. Rate and mechanism of the photoreduction of birnessite (MnO2) nanosheets

    PubMed Central

    Marafatto, Francesco Femi; Strader, Matthew L.; Gonzalez-Holguera, Julia; Schwartzberg, Adam; Gilbert, Benjamin; Peña, Jasquelin

    2015-01-01

    The photoreductive dissolution of Mn(IV) oxide minerals in sunlit aquatic environments couples the Mn cycle to the oxidation of organic matter and fate of trace elements associated with Mn oxides, but the intrinsic rate and mechanism of mineral dissolution in the absence of organic electron donors is unknown. We investigated the photoreduction of δ-MnO2 nanosheets at pH 6.5 with Na or Ca as the interlayer cation under 400-nm light irradiation and quantified the yield and timescales of Mn(III) production. Our study of transient intermediate states using time-resolved optical and X-ray absorption spectroscopy showed key roles for chemically distinct Mn(III) species. The reaction pathway involves (i) formation of Jahn–Teller distorted Mn(III) sites in the octahedral sheet within 0.6 ps of photoexcitation; (ii) Mn(III) migration into the interlayer within 600 ps; and (iii) increased nanosheet stacking. We propose that irreversible Mn reduction is coupled to hole-scavenging by surface water molecules or hydroxyl groups, with associated radical formation. This work demonstrates the importance of direct MnO2 photoreduction in environmental processes and provides a framework to test new hypotheses regarding the role of organic molecules and metal species in photochemical reactions with Mn oxide phases. The timescales for the production and evolution of Mn(III) species and a catalytic role for interlayer Ca2+ identified here from spectroscopic measurements can also guide the design of efficient Mn-based catalysts for water oxidation. PMID:25825757

  4. Fe-species-loaded mesoporous MnO2 superstructural requirements for enhanced catalysis.

    PubMed

    Huang, Ruting; Liu, Yanyu; Chen, Zhiwen; Pan, Dengyu; Li, Zhen; Wu, Minghong; Shek, Chan-Hung; Wu, C M Lawrence; Lai, Joseph K L

    2015-02-25

    In this work, a novel catalyst, Fe-species-loaded mesoporous manganese dioxide (Fe/M-MnO2) urchinlike superstructures, has been fabricated successfully in a two-step technique. First, mesoporous manganese dioxide (M-MnO2) urchinlike superstructures have been synthesized by a facile method on a soft interface between CH2Cl2 and H2O without templates. Then the M-MnO2-immobilized iron oxide catalyst was obtained through wetness impregnation and calcination. Microstructural analysis indicated that the M-MnO2 was composed of urchinlike hollow submicrospheres assembled by nanorod building blocks with rich mesoporosity. The Fe/M-MnO2 retained the hollow submicrospheres, which were covered by hybridized composites with broken and shortened MnO2 nanorods. Energy-dispersive X-ray microanalysis was used to determine the availability of Fe loading processes and the homogeneity of Fe in Fe/M-MnO2. Catalytic performances of the M-MnO2 and Fe/M-MnO2 were evaluated in catalytic wet hydrogen peroxide oxidation of methylene blue (MB), a typical organic pollutant in dyeing wastewater. The catalytic degradation displayed highly efficient discoloration of MB when using the Fe/M-MnO2 catalyst, e.g., ca. 94.8% of MB was decomposed when the reaction was conducted for 120 min. The remarkable stability of this Fe/M-MnO2 catalyst in the reaction medium was confirmed by an iron leaching test and reuse experiments. Mechanism analysis revealed that the hydroxyl free radical was responsible for the removal of MB and catalyzed by M-MnO2 and Fe/M-MnO2. MB was transformed into small organic compounds and then further degraded into CO2 and H2O. The new insights obtained in this study will be beneficial for the practical applications of heterogeneous catalysts in wastewater treatments. PMID:25626157

  5. 3D hierarchical MnO2 nanorod/welded Ag-nanowire-network composites for high-performance supercapacitor electrodes.

    PubMed

    Qiao, Zhensong; Yang, Xiaopeng; Yang, Shuhua; Zhang, Liqiang; Cao, Bingqiang

    2016-06-28

    3D MnO2 nanorod/welded Ag-nanowire-network supercapacitor electrodes were prepared. Welding treatment of the Ag nanowire-network leads to low resistance and long lifetime. Galvanostatic charge/discharge (GCD) induces an ever-lasting morphology changing from flower-like to honeycomb-like for MnO2, which manifests as increasing specific capacitance to 663.4 F g(-1) after 7000 GCD cycles. PMID:27263832

  6. An investigation of Cr(VI) removal with metallic iron in the co-presence of sand and/or MnO2.

    PubMed

    Gheju, M; Balcu, I; Vancea, C

    2016-04-01

    This study focused on the influence of sand and/or MnO2 co-presence on the mechanism and kinetics of Cr(VI) removal with Fe(0). The process was investigated under acidic and well-mixed conditions, over the temperature range of 6-32 °C. It was shown that both mechanism and kinetics of the removal process were highly dependent on composition and dose of reactive mixture added to Cr(VI) solution. At 22 °C, indirect chemical reduction with Fe(II) was the main removal path in H2O-Fe(0)-Cr(VI) and H2O-Fe(0)-Sand-Cr(VI) system, while in H2O-Fe(0)-MnO2-Cr(VI) and H2O-Fe(0)-MnO2-Sand-Cr(VI) system removal of Cr(VI) occurred mainly via adsorption on MnO2. The pseudo zero-order kinetic model provided the best match for H2O-Fe(0)-Cr(VI) and H2O-Fe(0)-Sand-Cr(VI) system, while in H2O-Fe(0)-MnO2-Cr(VI) and H2O-Fe(0)-MnO2-Sand-Cr(VI) system the process fitted well to the pseudo second-order model. Temperature influenced the efficiency and kinetics of the process in all investigated systems, and the removal mechanism only in H2O-Fe(0)-MnO2-Cr(VI) and H2O-Fe(0)-MnO2-Sand-Cr(VI) system. PMID:26826456

  7. One-Step Synthesis of Single-Layer MnO2 Nanosheets with Multi-Role Sodium Dodecyl Sulfate for High-Performance Pseudocapacitors.

    PubMed

    Liu, Zhenning; Xu, Kongliang; Sun, Hang; Yin, Shengyan

    2015-05-13

    A template-free, one-step and one-phase synthesis of single-layer MnO2 nanosheets has been developed via a redox reaction between KMnO4 and sodium dodecyl sulfate (SDS). The successful formation of single-layer MnO2 nanosheets has been confirmed by the characteristic absorption around 374 nm and the typical thickness of ~0.95 nm. The slow redox reaction controlled by the gradual hydrolysis of SDS is found to be the key factor for the successful formation of single-layer nanosheets. SDS not only serves as the precursor of dodecanol to reduce KMnO4 , but also aids the formation of single-layer MnO2 nanosheets as a structure-inducing agent. The resultant single-layer MnO2 nanosheets possess superior specific capacitance, which can be attributed to the extended surface and high porosity of MnO2 nanosheets on the electrode. The MnO2 nanosheets also show excellent durability, retaining 91% of the starting capacitance after 10 000 charge/discharge cycles. Moreover, the symmetric pseudocapacitor based on the synthesized single-layer MnO2 nanosheets exhibits a high specific capacitance, indicating great potential for real energy storage. Therefore, it has been demonstrated for the first time that a single readily available reagent, SDS, can play multiple roles in reducing KMnO4 to conveniently yield single-layer MnO2 nanosheets as a high-performance pseudocapacitive material. PMID:25565035

  8. Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

    PubMed Central

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-01-01

    Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm−2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm−2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms. PMID:25765731

  9. Porous honeycomb structures formed from interconnected MnO2 sheets on CNT-coated substrates for flexible all-solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Ko, Wen-Yin; Chen, You-Feng; Lu, Ke-Ming; Lin, Kuan-Jiuh

    2016-01-01

    The use of lightweight and easily-fabricated MnO2/carbon nanotube (CNT)-based flexible networks as binder-free electrodes and a polyvinyl alcohol/H2SO4 electrolyte for the formation of stretchable solid-state supercapacitors was examined. The active electrodes were fabricated from 3D honeycomb porous MnO2 assembled from cross-walled and interconnected sheet-architectural MnO2 on CNT-based plastic substrates (denoted as honeycomb MnO2/CNT textiles).These substrates were fabricated through a simple two-step procedure involving the coating of multi-walled carbon nanotubes (MWCNTs) onto commercial textiles by a dipping-drying process and subsequent electrodeposition of the interconnected MnO2 sheets onto the MWCNT-coated textile. With such unique MnO2 architectures integrated onto CNT flexible films, good performance was achieved with a specific capacitance of 324 F/g at 0.5 A/g. A maximum energy density of 7.2 Wh/kg and a power density as high as 3.3 kW/kg were exhibited by the honeycomb MnO2/CNT network device, which is comparable to the performance of other carbon-based and metal oxide/carbon-based solid-state supercapacitor devices. Specifically, the long-term cycling stability of this material is excellent, with almost no loss of its initial capacitance and good Coulombic efficiency of 82% after 5000 cycles. These impressive results identify these materials as a promising candidate for use in environmentally friendly, low-cost, and high-performance flexible energy-storage devices.

  10. Genetically Engineered Phage-Templated MnO2 Nanowires: Synthesis and Their Application in Electrochemical Glucose Biosensor Operated at Neutral pH Condition.

    PubMed

    Han, Lei; Shao, Changxu; Liang, Bo; Liu, Aihua

    2016-06-01

    To conveniently obtain one-dimensional MnO2 nanowires (NWs) with controlled structure and unique properties for electron transfer, the genetically engineered M13 phages were used as templates for precise nucleation and growth of MnO2 crystals in filamentous phage scaffolds, via the spontaneous oxidation of Mn(2+) in alkaline solution. It was found that the morphology of NWs could be tailored by the surface charge of M13 mutants. MnO2 crystals were uniformly distributed on the surface of negatively charged tetraglutamate-fused phage (M13-E4), significantly different from irregular MnO2 agglomeration on the weakly negatively charged wild-type phage and positively charged tetraarginine-fused phage. The as-synthesized M13-E4@MnO2 NWs could catalyze the electro-oxidation of H2O2 at neutral pH. To demonstrate the superiority of the electrocatalytic activity in the solution containing plenty of chloride ions at neutral pH, both glucose oxidase and as-prepared MnO2 NWs were used for fabricating the glucose biosensor. The proposed biosensor showed a wide linear range (5 μM to 2 mM glucose), a low limit of detection of 1.8 μM glucose (S/N = 3), good interassay and intra-assay reproducibility and satisfactory storage stability. Due to the superiorities of synthesis and electrochemical performance, the as-prepared MnO2 NWs are promising for applications in electrocatalysis, electrochemical sensor, and supercapacitor. PMID:27228383

  11. Porous honeycomb structures formed from interconnected MnO2 sheets on CNT-coated substrates for flexible all-solid-state supercapacitors.

    PubMed

    Ko, Wen-Yin; Chen, You-Feng; Lu, Ke-Ming; Lin, Kuan-Jiuh

    2016-01-01

    The use of lightweight and easily-fabricated MnO2/carbon nanotube (CNT)-based flexible networks as binder-free electrodes and a polyvinyl alcohol/H2SO4 electrolyte for the formation of stretchable solid-state supercapacitors was examined. The active electrodes were fabricated from 3D honeycomb porous MnO2 assembled from cross-walled and interconnected sheet-architectural MnO2 on CNT-based plastic substrates (denoted as honeycomb MnO2/CNT textiles).These substrates were fabricated through a simple two-step procedure involving the coating of multi-walled carbon nanotubes (MWCNTs) onto commercial textiles by a dipping-drying process and subsequent electrodeposition of the interconnected MnO2 sheets onto the MWCNT-coated textile. With such unique MnO2 architectures integrated onto CNT flexible films, good performance was achieved with a specific capacitance of 324 F/g at 0.5 A/g. A maximum energy density of 7.2 Wh/kg and a power density as high as 3.3 kW/kg were exhibited by the honeycomb MnO2/CNT network device, which is comparable to the performance of other carbon-based and metal oxide/carbon-based solid-state supercapacitor devices. Specifically, the long-term cycling stability of this material is excellent, with almost no loss of its initial capacitance and good Coulombic efficiency of 82% after 5000 cycles. These impressive results identify these materials as a promising candidate for use in environmentally friendly, low-cost, and high-performance flexible energy-storage devices. PMID:26726724

  12. Porous honeycomb structures formed from interconnected MnO2 sheets on CNT-coated substrates for flexible all-solid-state supercapacitors

    PubMed Central

    Ko, Wen-Yin; Chen, You-Feng; Lu, Ke-Ming; Lin, Kuan-Jiuh

    2016-01-01

    The use of lightweight and easily-fabricated MnO2/carbon nanotube (CNT)-based flexible networks as binder-free electrodes and a polyvinyl alcohol/H2SO4 electrolyte for the formation of stretchable solid-state supercapacitors was examined. The active electrodes were fabricated from 3D honeycomb porous MnO2 assembled from cross-walled and interconnected sheet-architectural MnO2 on CNT-based plastic substrates (denoted as honeycomb MnO2/CNT textiles).These substrates were fabricated through a simple two-step procedure involving the coating of multi-walled carbon nanotubes (MWCNTs) onto commercial textiles by a dipping-drying process and subsequent electrodeposition of the interconnected MnO2 sheets onto the MWCNT-coated textile. With such unique MnO2 architectures integrated onto CNT flexible films, good performance was achieved with a specific capacitance of 324 F/g at 0.5 A/g. A maximum energy density of 7.2 Wh/kg and a power density as high as 3.3 kW/kg were exhibited by the honeycomb MnO2/CNT network device, which is comparable to the performance of other carbon-based and metal oxide/carbon-based solid-state supercapacitor devices. Specifically, the long-term cycling stability of this material is excellent, with almost no loss of its initial capacitance and good Coulombic efficiency of 82% after 5000 cycles. These impressive results identify these materials as a promising candidate for use in environmentally friendly, low-cost, and high-performance flexible energy-storage devices. PMID:26726724

  13. Two-step approach of fabrication of three-dimensional MnO2-graphene-carbon nanotube hybrid as a binder-free supercapacitor electrode

    NASA Astrophysics Data System (ADS)

    Xiong, Chuanyin; Li, Tiehu; Dang, Alei; Zhao, Tingkai; Li, Hao; Lv, Huiqin

    2016-02-01

    This paper describes the fabrication and characterization of a three-dimensional (3D) MnO2-graphene (GR)-CNT hybrid obtained by combining electrochemical deposition (ELD)-electrophoretic deposition (EPD) and chemical vapor deposition (CVD). Firstly, 3D MnO2-graphene oxide (GO) is fabricated via ELD-EPD. Secondly, the catalyst and xylene are mixed with solution of certain concentration. Thirdly, catalyst is loaded on the surface of MnO2-GO when the solution is sprayed into the furnace. Forth, MnO2-GO is restored to MnO2-GR at high temperature, meanwhile, MnO2-GR is served as a substrate to grow CNT, which is beneficial to provide high speed channel for carrier and obtain pseudocapacitance of MnO2. The as-prepared hybrid is characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray Diffraction (XRD) and Raman spectroscopy (Raman), and their supercapacitor properties are also investigated. The results show that a high specific capacitance of 330.75 F g-1 and high energy density of 36.68 Wh kg-1 while maintaining high power density of 8000 W kg-1 at a scan rate of 200 mV s-1. Furthermore, the hybrid displays a high specific capacitance of 187.53 F g-1 at ultrahigh scan rate of 400 mV s-1. These attractive results demonstrate that the hybrid is a promising electrode material for high performance supercapacitors.

  14. Fast and stable redox reactions of MnO2/CNT hybrid electrodes for dynamically stretchable pseudocapacitors

    NASA Astrophysics Data System (ADS)

    Gu, Taoli; Wei, Bingqing

    2015-07-01

    Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid electrodes. The extremely small relaxation time constant of less than 0.15 s indicates a fast redox reaction at the MnO2/CNT hybrid electrodes, securing a stable electrochemical performance for the dynamically stretchable pseudocapacitors. This finding and the fundamental understanding gained from the pseudo-capacitive behavior coupled with mechanical deformation under a dynamic stretching mode would provide guidance to further improve their overall performance including a higher power density than LIBs, a higher energy density than EDLCs, and a long-life cycling stability. Most importantly, these results will potentially accelerate the applications of stretchable pseudocapacitors for flexible and biomedical electronics.Pseudocapacitors, which are energy storage devices that take advantage of redox reactions to store electricity, have a different charge storage mechanism compared to lithium-ion batteries (LIBs) and electric double-layer capacitors (EDLCs), and they could realize further gains if they were used as stretchable power sources. The realization of dynamically stretchable pseudocapacitors and understanding of the underlying fundamentals of their mechanical-electrochemical relationship have become indispensable. We report herein the electrochemical performance of dynamically stretchable pseudocapacitors using buckled MnO2/CNT hybrid electrodes. The extremely small relaxation time constant of less than 0.15 s indicates a fast redox reaction at the MnO2/CNT hybrid electrodes, securing a stable electrochemical performance for the dynamically stretchable pseudocapacitors. This finding and the fundamental understanding gained from the pseudo-capacitive behavior coupled with mechanical deformation under a dynamic stretching mode would provide guidance to further improve their overall performance including a higher power density than LIBs, a higher energy density than EDLCs, and a long-life cycling stability. Most importantly, these results will potentially accelerate the applications of stretchable pseudocapacitors for flexible and biomedical electronics. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02310f

  15. Interlinked multiphase Fe-doped MnO2 nanostructures: a novel design for enhanced pseudocapacitive performance

    NASA Astrophysics Data System (ADS)

    Wang, Ziya; Wang, Fengping; Li, Yan; Hu, Jianlin; Lu, Yanzhen; Xu, Mei

    2016-03-01

    Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g-1 even under a high mass loading (~5 mg cm-2). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm-3) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g-1. The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices.Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g-1 even under a high mass loading (~5 mg cm-2). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm-3) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g-1. The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08857g

  16. Identification of a c-Type Cytochrome Specific for Manganese Dioxide (MnO2) Reduction in Anaeromyxobacter dehalogenans Strain 2CP-C

    NASA Astrophysics Data System (ADS)

    Pfiffner, S. M.; Nissen, S.; Liu, X.; Chourey, K.; Vishnivetskaya, T. A.; Hettich, R.; Loeffler, F.

    2014-12-01

    Anaeromyxobacter dehalogenans is a metabolically versatile Deltaproteobacterium and conserves energy from the reduction of various electron acceptors, including insoluble MnO2 and ferric oxides/oxyhydroxides (FeOOH). The goal of this study was to identify c-type cytochromes involved in electron transfer to MnO2. The characterization of deletion mutants has revealed a number of c-type cytochromes involved in electron transfer to solid metal oxides in Shewanella spp. and Geobacter spp; however, a genetic system for Anaeromyxobacter is not available. The A. dehalogenans str. 2CP-C genome encodes 68 putative c-type cytochromes, which all lack functional assignments. To identify c-type cytochromes involved in electron transfer to solid MnO2, protein expression profiles of A. dehalogenans str. 2CP-C cells grown with acetate as electron donor and MnO2, ferric citrate, FeOOH, nitrate or fumarate as electron acceptors were compared. Whole cell proteomes were analyzed after trypsin proteolysis using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Distinct c-type cytochrome expression patterns were observed with cells grown with different electron acceptors. A. dehalogenans str. 2CP-C grown with MnO2 expressed 25 out of the 68 c-type cytochromes encoded on the genome. The c-type cytochrome Adeh_1278 was only expressed in strain 2CP-C grown with MnO2. Reverse transcription PCR confirmed that the Adeh_1278 gene was transcribed in MnO2-grown cells but not in cells grown with other terminal electron acceptors. The expression of the Adeh_1278 gene correlated with Mn(IV) reduction activity. Adeh_1278 has three heme binding motifs and is predicted to be located in the periplasm. The identification of Adeh_1278 as a protein uniquely expressed when MnO2 serves as electron acceptor suggests its utility as a biomarker for MnO2 reduction. This example demonstrates the value of the LC-MS/MS approach for identifying specific proteins of interest and making functional assignments to proteins, including c-type cytochromes that have not been characterized. The distinctive expression of c-type cytochromes in response to growth with different terminal electron acceptors offers opportunities for functional (i.e., activity) in situ monitoring using metaproteomics or transcript-targeted approaches.

  17. Hierarchical core/shell structure of MnO2@polyaniline composites grown on carbon fiber paper for application in pseudocapacitors.

    PubMed

    Yang, MinHo; Hong, Seok Bok; Choi, Bong Gill

    2015-11-28

    Hierarchical core/shell structured arrays of MnO2@polyaniline (PANI) nanosheets are successfully deposited on the surface of carbon fiber paper (CFP) by a two-step method of a redox reaction-assisted deposition of MnO2 and post electrodeposition of PANI. The CFP is used as a three-dimensional (3D) current collector to ensure 3D transport of ions and electrons with a large surface area. In addition, the electrodeposition technique enables conformal and thin coating of a layer of PANI across the entire MnO2 nanosheet. The MnO2@PANI on the CFP shows a unique architecture for efficient ion diffusion pathways in hierarchical porous structures and rapid electron transfer through PANI coated layers. The MnO2@PANI/CFP can be applied as a binder- and carbon-free electrode for supercapacitors. Evaluation of the electrochemical performance revealed that the as-prepared electrodes have a high value of specific capacitance (437 F g(-1) at 1 A g(-1)), high rate capability (62.4% retention at 15 A g(-1)), and good cycle life (∼100% at sequential current densities of 1 and 5 A g(-1) over 3000 cycles). PMID:26486195

  18. A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte.

    PubMed

    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. PMID:27241801

  19. Suppressing the Coffee-Ring Effect in Semitransparent MnO2 Film for a High-Performance Solar-Powered Energy Storage Window.

    PubMed

    Jin, Huanyu; Qian, Jiasheng; Zhou, Limin; Yuan, Jikang; Huang, Haitao; Wang, Yu; Tang, Wing Man; Chan, Helen Lai Wa

    2016-04-13

    We introduce a simple and effective method to deposit a highly uniform and semitransparent MnO2 film without coffee-ring effect (CRE) by adding ethanol into MnO2 ink for transparent capacitive energy storage devices. By carefully controlling the amount of ethanol added in the MnO2 droplet, we could significantly reduce the CRE and thus improve the film uniformity. The electrochemical properties of supercapacitor (SC) devices using semitransparent MnO2 film electrodes with or without CRE were measured and compared. The SC device without CRE shows a superior capacitance, high rate capability, and lower contact resistance. The CRE-free device could achieve a considerable volumetric capacitance of 112.2 F cm(-3), resulting in a high volumetric energy density and power density of 10 mWh cm(-3) and 8.6 W cm(-3), respectively. For practical consideration, both flexible SC and large-area rigid SC devices were fabricated to demonstrate their potential for flexible transparent electronic application and capacitive energy-storage window application. Moreover, a solar-powered energy storage window which consists of a commercial solar cell and our studied semitransparent MnO2-film-based SCs was assembled. These SCs could be charged by the solar cell and light up a light emitting diode (LED), demonstrating their potential for self-powered systems and energy-efficient buildings. PMID:26953596

  20. 3D hierarchical assembly of ultrathin MnO2 nanoflakes on silicon nanowires for high performance micro-supercapacitors in Li- doped ionic liquid

    PubMed Central

    Dubal, Deepak P.; Aradilla, David; Bidan, Gérard; Gentile, Pascal; Schubert, Thomas J.S.; Wimberg, Jan; Sadki, Saïd; Gomez-Romero, Pedro

    2015-01-01

    Building of hierarchical core-shell hetero-structures is currently the subject of intensive research in the electrochemical field owing to its potential for making improved electrodes for high-performance micro-supercapacitors. Here we report a novel architecture design of hierarchical MnO2@silicon nanowires (MnO2@SiNWs) hetero-structures directly supported onto silicon wafer coupled with Li-ion doped 1-Methyl-1-propylpyrrolidinium bis(trifluromethylsulfonyl)imide (PMPyrrBTA) ionic liquids as electrolyte for micro-supercapacitors. A unique 3D mesoporous MnO2@SiNWs in Li-ion doped IL electrolyte can be cycled reversibly across a voltage of 2.2 V and exhibits a high areal capacitance of 13 mFcm−2. The high conductivity of the SiNWs arrays combined with the large surface area of ultrathin MnO2 nanoflakes are responsible for the remarkable performance of these MnO2@SiNWs hetero-structures which exhibit high energy density and excellent cycling stability. This combination of hybrid electrode and hybrid electrolyte opens up a novel avenue to design electrode materials for high-performance micro-supercapacitors. PMID:25985388

  1. Self-Assembly of Mesoporous Nanotubes Assembled from Interwoven Ultrathin Birnessite-type MnO2 Nanosheets for Asymmetric Supercapacitors

    PubMed Central

    Huang, Ming; Zhang, Yuxin; Li, Fei; Zhang, Lili; Ruoff, Rodney S.; Wen, Zhiyu; Liu, Qing

    2014-01-01

    Porous nanotubes comprised of MnO2 nanosheets were fabricated with a one-pot hydrothermal method using polycarbonate membrane as the template. The diameter and thickness of nanotubes can be controlled by choice of the membrane pore size and the chemistry. The porous MnO2 nanotubes were used as a supercapacitor electrode. The specific capacitance in a three-electrode system was 365 F g−1 at a current density of 0.25 A g−1 with capacitance retention of 90.4% after 3000 cycles. An asymmetric supercapacitor with porous MnO2 nanotubes as the positive electrode and activated graphene as the negative electrode yielded an energy density of 22.5 Wh kg−1 and a maximum power density of 146.2 kW kg−1; these values exceeded those reported for other MnO2 nanostructures. The supercapacitor performance was correlated with the hierarchical structure of the porous MnO2 nanotubes. PMID:24464344

  2. 3D hierarchical assembly of ultrathin MnO2 nanoflakes on silicon nanowires for high performance micro-supercapacitors in Li- doped ionic liquid

    NASA Astrophysics Data System (ADS)

    Dubal, Deepak P.; Aradilla, David; Bidan, Gérard; Gentile, Pascal; Schubert, Thomas J. S.; Wimberg, Jan; Sadki, Saïd; Gomez-Romero, Pedro

    2015-05-01

    Building of hierarchical core-shell hetero-structures is currently the subject of intensive research in the electrochemical field owing to its potential for making improved electrodes for high-performance micro-supercapacitors. Here we report a novel architecture design of hierarchical MnO2@silicon nanowires (MnO2@SiNWs) hetero-structures directly supported onto silicon wafer coupled with Li-ion doped 1-Methyl-1-propylpyrrolidinium bis(trifluromethylsulfonyl)imide (PMPyrrBTA) ionic liquids as electrolyte for micro-supercapacitors. A unique 3D mesoporous MnO2@SiNWs in Li-ion doped IL electrolyte can be cycled reversibly across a voltage of 2.2 V and exhibits a high areal capacitance of 13 mFcm-2. The high conductivity of the SiNWs arrays combined with the large surface area of ultrathin MnO2 nanoflakes are responsible for the remarkable performance of these MnO2@SiNWs hetero-structures which exhibit high energy density and excellent cycling stability. This combination of hybrid electrode and hybrid electrolyte opens up a novel avenue to design electrode materials for high-performance micro-supercapacitors.

  3. Application of biomass-derived flexible carbon cloth coated with MnO2 nanosheets in supercapacitors

    NASA Astrophysics Data System (ADS)

    He, Shuijian; Chen, Wei

    2015-10-01

    Successful application of inexpensive energy storage devices lies in the exploitation of fabrication approaches that are based on cost-efficient materials and that can be easily scaled up. Here, inexpensive textile weaved by natural flax fiber is selected as raw material in preparing flexible and binder-free electrode material for supercapacitors. Although carbon fiber cloth obtained from the direct carbonization of flax textile exhibits a low specific capacitance of 0.78 F g-1, carbon fiber cloth electrode shows a very short relaxation time of 39.1 m s and good stability with almost 100% capacitance retaining after 104 cycles at 5 A g-1. To extend the application of the resulting carbon cloth in supercapacitor field, a layer of MnO2 nanosheets is deposited on the surface of carbon fiber via in situ redox reaction between carbon and KMnO4. The specific capacitance of MnO2 reaches 683.73 F g-1 at 2 A g-1 and still retains 269.04 F g-1 at 300 A g-1, indicating the excellent rate capacitance performance of the carbon cloth/MnO2 hybrids. The present study shows that carbon cloth derived from flax textile can provide a low-cost material platform for the facile, cost-efficient and large scale fabrication of binder-free electrode materials for energy storage devices.

  4. Interlinked multiphase Fe-doped MnO2 nanostructures: a novel design for enhanced pseudocapacitive performance.

    PubMed

    Wang, Ziya; Wang, Fengping; Li, Yan; Hu, Jianlin; Lu, Yanzhen; Xu, Mei

    2016-03-24

    Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g(-1) even under a high mass loading (∼5 mg cm(-2)). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm(-3)) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g(-1). The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices. PMID:26977698

  5. The evolution mechanism of defect dipoles and high strain in MnO2-doped KNN lead-free ceramics

    NASA Astrophysics Data System (ADS)

    Zhao, Zhihao; Dai, Yejing; Li, Xiaolei; Zhao, Zhe; Zhang, Xiaowen

    2016-04-01

    Defect dipoles in acceptor-doped (K0.5Na0.5)NbO3-based ceramics have a significant influence on their electrical properties. The present study examined the influence of the sintering atmosphere on the electrical properties of MnO2-doped (K0.5Na0.5)NbO3. The poled and aged samples sintered in the Ar atmosphere depicted unusual behavior related to the formation of defect dipoles ( M n2+ N b ‴ - VO .. ) ' , aligned in the poling direction having larger polarity. The S-E loop of the poled and aged MnO2-doped (K0.5Na0.5)NbO3 ceramics sintered in the Ar atmosphere revealed larger strains in the poling direction and restrained strains in the opposite direction. Furthermore, it is observed that the unipolar electro-strain could reach 0.28% (d33* = 800 pm/V) at 3.5 kV/mm, a value nearly 5.6-fold higher than those obtained in the air atmosphere (0.05%). This method based on the sintering atmosphere and process control provides a promising way to obtain substantial electro-strain values suitable for applications in high-displacement actuators.

  6. Leaching and separation of zinc from the black paste of spent MnO2-Zn dry cell batteries.

    PubMed

    El-Nadi, Y A; Daoud, J A; Aly, H F

    2007-05-01

    Spent batteries represent a source of hazardous materials when discarded without appropriate treatment. Investigations on the recovery of zinc from the black paste of spent MnO(2)-Zn cell batteries were carried out. Leaching of zinc and manganese from the black paste of spent batteries using sulfuric or hydrochloric acid solutions was studied. It was found that leaching with sulfuric acid solution is more efficient than with HCl solution. Different parameters affecting the leaching of Zn(II) and Mn(II) with sulfuric acid were further studied. Extraction of Zn(II) and Mn(II) from the leaching sulfate medium by bis(2,4,4-trimethylpentyl) dithiophosphinic acid (CYANEX 301) diluted with kerosene was investigated. The factors affecting the extraction process, separately studied, include the effect of contact time, sulfuric acid concentration, CYANEX 301 concentration, phase ratio as well as temperature. The results indicated that, from sulfate medium, Zn(II) is more extracted than Mn(II). Selective stripping of Zn(II) was obtained using 5M HCl. Application of the method on the leaching sulfate solution of the spent MnO(2)-Zn dry cell black paste show the efficiency of the process, where the extraction and stripping of Zn(II) are 98% and 99%, respectively. PMID:17049161

  7. The design of an Fe-12Mn-O.2Ti alloy steel for low temperature use

    NASA Technical Reports Server (NTRS)

    Hwang, S. K.; Morris, J. W., Jr.

    1977-01-01

    An investigation was made to improve the low temperature mechanical properties of Fe-8 approximately 12% Mn-O 2Ti alloy steels. A two-phase(alpha + gamma) tempering in combination with cold working or hot working was identified as an effective treatment. A potential application as a Ni-free cryogenic steel was shown for this alloy. It was also shown that an Fe-8Mn steel could be grain-refined by a purely thermal treatment because of its dislocated martensitic structure and absence of epsilon phase. A significant reduction of the ductile-brittle transition temperature was obtained in this alloy. The nature and origin of brittle fracture in Fe-Mn alloys were also investigated. Two embrittling regions were found in a cooling curve of an Fe-12Mn-O 2Ti steel which was shown to be responsible for intergranular fracture. Auger electron spectroscopy identified no segregation during solution-annealing treatment. Avoiding the embrittling zones by controlled cooling led to a high cryogenic toughness in a solution-annealed condition.

  8. Constraints on the utility of MnO2 cartridge method for the extraction of radionuclides: A case study using 234Th

    USGS Publications Warehouse

    Baskaran, M.; Swarzenski, P.W.; Biddanda, B.A.

    2009-01-01

    [1] Large volume (102-103 L) seawater samples are routinely processed to investigate the partitioning of particle reactive radionuclides and Ra between solution and size-fractionated suspended particulate matter. One of the most frequently used methods to preconcentrate these nuclides from such large volumes involves extraction onto three filter cartridges (a prefilter for particulate species and two MnO2-coated filters for dissolved species) connected in series. This method assumes that the extraction efficiency is uniform for both MnO2-coated cartridges, that no dissolved species are removed by the prefilter, and that any adsorbed radionuclides are not desorbed from the MnO2-coated cartridges during filtration. In this study, we utilized 234Th-spiked coastal seawater and deionized water to address the removal of dissolved Th onto prefilters and MnO2-coated filter cartridges. Experimental results provide the first data that indicate (1) a small fraction of dissolved Th (<6%) can be removed by the prefilter cartridge; (2) a small fraction of dissolved Th (<5%) retained by the MnO2 surface can also be desorbed, which undermines the assumption of uniform extraction efficiency for Th; and (3) the absolute and relative extraction efficiencies can vary widely. These experiments provide insight on the variability of the extraction efficiency of MnO 2-coated filter cartridges by comparing the relative and absolute efficiencies and recommend the use of a constant efficiency on the combined activity from two filter cartridges connected in series for future studies of dissolved 234Th and other radionuclides in natural waters using sequential filtration/extraction methods. ?? 2009 by the American Geophysical Union.

  9. A Facile Method for in Situ Preparation of the MnO2/LaMnO3 Catalyst for the Removal of Toluene.

    PubMed

    Si, Wenzhe; Wang, Yu; Zhao, Shen; Hu, Fangyun; Li, Junhua

    2016-04-19

    MOx/ABO3 is a promising catalyst for the high-efficiency removal of volatile organic compounds. However, this catalyst is limited on practical applications due to its complex synthesis procedure and high cost. In this work, the MnO2/LaMnO3 catalyst was prepared in situ using a facile one-step method for the first time, in which partial La cations were selectively removed from three dimensionally chain-like ordered macroporous (3DOM) LaMnO3 material. After selective removal, the obtained MnO2/LaMnO3 sample expressed an excellent catalytic performance on toluene oxidation. Toluene could be completely oxidized into CO2 and H2O at 290 °C over the MnO2/LaMnO3 catalyst with a toluene/oxygen molar ratio of 1/100 and a space velocity of 120 000 mL/(g h). In addition, the apparent activation energy value of MnO2/LaMnO3 was 57 kJ/mol, which was lower than those of other metal oxides catalysts. According to O2-TPD and XPS results, it is concluded that the high catalytic performance of MnO2/LaMnO3 was mainly associated with the large amount of oxygen species and the excellent lattice oxygen mobility. MnO2/LaMnO3 is a promising catalyst for the practical removal of volatile organic compounds due to its high efficiency, good stability, low cost, and convenient preparation. PMID:26886715

  10. Morphological and crystalline evolution of nanostructured MnO2 and its application in lithium--air batteries.

    PubMed

    Truong, Tu T; Liu, Yuzi; Ren, Yang; Trahey, Lynn; Sun, Yugang

    2012-09-25

    Single-crystal α-MnO(2) nanotubes have been successfully synthesized by microwave-assisted hydrothermal of potassium permanganate in the presence of hydrochloric acid. The growth mechanism including the morphological and crystalline evolution has been carefully studied with time-dependent X-ray diffraction, electron microscopy, and controlled synthesis. The as-synthesized MnO(2) nanostructures are incorporated in air cathodes of lithium--air batteries as electrocatalysts for the oxygen reduction and evolution reactions. The characterization reveals that the electrodes made of single-crystalline α-MnO(2) nanotubes exhibit much better stability than those made of α-MnO(2) nanowires and δ-MnO(2) nanosheet-based microflowers in both charge and discharge processes. PMID:22866870

  11. Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO2) and adsorption of remazol reactive dye

    NASA Astrophysics Data System (ADS)

    Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

    2015-09-01

    Nanoporous amorphous-MnO2 was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH3COO)2.4H2O) in 0.1 M KMnO4. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO2 bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO2. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye on 0.2g synthesized nanoporous amorphous-MnO2 showed 99 - 100% decolorization.

  12. Controlled partial-exfoliation of graphite foil and integration with MnO2 nanosheets for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Song, Yu; Feng, Dong-Yang; Liu, Tian-Yu; Li, Yat; Liu, Xiao-Xia

    2015-02-01

    Here we demonstrate a controlled two-step partial exfoliation method to synthesize functionalized exfoliated graphite substrates. Ultrathin and functionalized graphene sheets anchoring on the graphite provide a large conductive surface area for loading pseudo-capacitive MnO2 nanosheets. The functionalized exfoliated graphite/MnO2 electrode achieved an excellent areal capacitance of 244 mF cm-2, corresponding to an estimated MnO2 based gravimetric capacitance of 1061 F g-1, which is just slightly lower than its theoretical value of 1110 F g-1. More importantly, the seamless integration of graphene sheets and the graphite substrate minimizes the contact resistance, and substantially improves the rate capability of pseudo-capacitive materials. The electrode retained 44.8% of its capacitance when the charging current density increased 50 times from 0.23 to 11.5 mA cm-2. This novel functionalized exfoliated graphite substrate serves as a promising supporting material that could address the relatively low electrical conductivity of various pseudo-capacitive materials, and increase the mass loading and rate capability of pseudo-capacitors.Here we demonstrate a controlled two-step partial exfoliation method to synthesize functionalized exfoliated graphite substrates. Ultrathin and functionalized graphene sheets anchoring on the graphite provide a large conductive surface area for loading pseudo-capacitive MnO2 nanosheets. The functionalized exfoliated graphite/MnO2 electrode achieved an excellent areal capacitance of 244 mF cm-2, corresponding to an estimated MnO2 based gravimetric capacitance of 1061 F g-1, which is just slightly lower than its theoretical value of 1110 F g-1. More importantly, the seamless integration of graphene sheets and the graphite substrate minimizes the contact resistance, and substantially improves the rate capability of pseudo-capacitive materials. The electrode retained 44.8% of its capacitance when the charging current density increased 50 times from 0.23 to 11.5 mA cm-2. This novel functionalized exfoliated graphite substrate serves as a promising supporting material that could address the relatively low electrical conductivity of various pseudo-capacitive materials, and increase the mass loading and rate capability of pseudo-capacitors. Electronic supplementary information (ESI) available: Calculations; digital photographs of flexible graphite foil, the primary exfoliation process, and the secondary exfoliation process; the CV profile of the primary exfoliation and the secondary exfoliation processes; the SEM image of graphite foil obtained after only second exfoliation; the AFM image of graphene on EG; XPS survey spectra of G, EG, and FEG; CVs of FEG from 100 to 10 000 mV s-1 the Mn 2p XPS spectrum; XRD spectra of FEG/MnO2 and FEG; the gravimetric specific capacitance of FEG/MnO2 at different current densities; constant current charge/discharge profiles of FEG/MnO2 at different current densities; SEM images of G/MnO2 and EG/MnO2. See DOI: 10.1039/c4nr06559j

  13. Combined Experimental and Computational Studies of a Na2 Ni1-x Cux Fe(CN)6 Cathode with Tunable Potential for Aqueous Rechargeable Sodium-Ion Batteries.

    PubMed

    Hung, Tai-Feng; Chou, Hung-Lung; Yeh, Yu-Wen; Chang, Wen-Sheng; Yang, Chang-Chung

    2015-10-26

    Herein, potential-tunable Na2 Ni1-x Cux Fe(CN)6 nanoparticles with three-dimensional frameworks and large interstitial spaces were synthesized as alternative cathode materials for aqueous sodium-ion batteries by controlling the molar ratio of Ni(II) to Cu(II) at ambient temperature. The influence of the value of x on the crystalline structure, lattice parameters, electrochemical properties, and charge transfer of the resultant compound was explored by using powder X-ray diffractometry, density functional theory, cyclic voltammetry, galvanostatic charge-discharge techniques, and Bader charge analysis. Of the various formulations investigated, that with x=0.25 delivered the highest reversible capacity, superior rate capability, and outstanding cycling performance. These attributes are ascribed to its unique face-centered cubic structure for facile sodium-ion insertion/extraction and the strong interactions between Cu and N atoms, which promote structural stability. PMID:26350587

  14. A high surface area tunnel-type α-MnO2 nanorod cathode by a simple solvent-free synthesis for rechargeable aqueous zinc-ion batteries

    NASA Astrophysics Data System (ADS)

    Alfaruqi, Muhammad Hilmy; Islam, Saiful; Gim, Jihyeon; Song, Jinju; Kim, Sungjin; Pham, Duong Tung; Jo, Jeonggeun; Xiu, Zhiliang; Mathew, Vinod; Kim, Jaekook

    2016-04-01

    Tunnel-type α-MnO2 with a nanorod morphology was prepared via a simple solvent-free synthesis method for use in aqueous zinc-ion battery (ZIB). This synthesis method produced α-MnO2 with a high BET surface area of 153 m2 g-1. α-MnO2 electrode demonstrated remarkable zinc storage properties (first and second discharge capacities of 323 and 270 mAh g-1 at 16 mA g-1) with good capacity retentions and rate capability. After charging within only 60 s, the α-MnO2 nanorod cathode delivered a considerable discharge capacity of 115 mAh g-1 when cycled at current density of 16 mA g-1.

  15. Ultrafine MnO2 nanoparticles decorated on graphene oxide as a highly efficient and recyclable catalyst for aerobic oxidation of benzyl alcohol.

    PubMed

    Hu, Zonggao; Zhao, Yafei; Liu, Jindun; Wang, Jingtao; Zhang, Bing; Xiang, Xu

    2016-12-01

    The highly active and selective aerobic oxidation of aromatic alcohols over earth-abundant, inexpensive and recyclable catalysts is highly desirable. We fabricated herein MnO2/graphene oxide (GO) composites by a facile in-situ growth approach at room temperature and used them in selective aerobic oxidation of benzyl alcohol to benzaldehyde. TEM, XRD, FTIR, XPS and N2 adsorption/desorption analysis were employed to systematically investigate the morphology, particle size, structure and surface properties of the catalysts. The 96.8% benzyl alcohol conversion and 100% benzaldehyde selectivity over the MnO2/GO (10/100) catalyst with well dispersive ultrafine MnO2 nanoparticles (ca. 3nm) can be obtained within 3h under 383K. Simultaneously, no appreciable loss of activity and selectivity occurred after recycling use up to six times. Due to their significant low cost, excellent catalytic performance, the MnO2/GO composites have huge application prospect in organic synthesis. PMID:27544446

  16. 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 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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02215d

  17. Synthesis of NASICON-type structured NaTi2(PO4)3-graphene nanocomposite as an anode for aqueous rechargeable Na-ion batteries

    NASA Astrophysics Data System (ADS)

    Pang, Gang; Yuan, Changzhou; Nie, Ping; Ding, Bing; Zhu, Jiajia; Zhang, Xiaogang

    2014-05-01

    A new solvothermal strategy combined with calcination has been developed to synthesize NaTi2(PO4)3-graphene nanocomposites. X-ray diffraction, thermogravimetric analysis, field-emission scanning electron microscopy and transmission electron microscopy were performed to characterize their microstructures and morphologies. It was found that NASICON-type structured NaTi2(PO4)3 nanoparticles with highly crystallinity were homogeneously anchored on the surface of conducting graphene nanosheets, forming a two-dimensional hybrid nanoarchitecture. A possible growth mechanism was also discussed based on time-dependent experiments. When used as anode materials for Na-ion batteries, the nanocomposites exhibited excellent electrochemical performance with high-rate capability and excellent cycling stability in 1 M Na2SO4 aqueous electrolyte. The electrode delivered high specific capacities of 110, 85, 65, 40 mA h g-1 at 2, 5, 10 and 20 C, respectively, and still retained 90% of the initial capacity after 100 cycles at 2 C.A new solvothermal strategy combined with calcination has been developed to synthesize NaTi2(PO4)3-graphene nanocomposites. X-ray diffraction, thermogravimetric analysis, field-emission scanning electron microscopy and transmission electron microscopy were performed to characterize their microstructures and morphologies. It was found that NASICON-type structured NaTi2(PO4)3 nanoparticles with highly crystallinity were homogeneously anchored on the surface of conducting graphene nanosheets, forming a two-dimensional hybrid nanoarchitecture. A possible growth mechanism was also discussed based on time-dependent experiments. When used as anode materials for Na-ion batteries, the nanocomposites exhibited excellent electrochemical performance with high-rate capability and excellent cycling stability in 1 M Na2SO4 aqueous electrolyte. The electrode delivered high specific capacities of 110, 85, 65, 40 mA h g-1 at 2, 5, 10 and 20 C, respectively, and still retained

  18. Electrochemical investigation of the role of MnO2 nanorod catalysts in water containing and anhydrous electrolytes for Li-O2 battery applications.

    PubMed

    Geaney, Hugh; O'Dwyer, Colm

    2015-03-14

    The electrochemical behaviour of MnO2 nanorod and Super P carbon based Li-O2 battery cathodes in water-containing sulfolane and anhydrous DMSO electrolytes are shown to be linked to specific discharge product formation. During discharge, large layered spherical agglomerates of LiOH were characteristically formed on the MnO2 cathodes while smaller, toroidal, spherical Li2O2 particles and films were formed on the Super P cathodes. In an anhydrous DMSO based electrolyte the LiOH structures were also found on cathodes discharged in the anhydrous electrolyte, suggesting that MnO2 initiates electrochemical decomposition of the DMSO electrolyte to form LiOH via H2O reactions with Li2O2. The LiOH crystals are uniquely formed on MnO2, and segregated to this phase even in mixed oxide-carbon cathodes. In contrast, no Li2O2 toroids were noted on Super P cathodes discharged in the DMSO based electrolytes. Instead, the morphology varied from smaller sheets (at high discharge current) to much larger agglomerates (at low discharge currents). In mixed carbon-MnO2 nanorod cathodes, the use of PVDF initiates H2O formation that affects discharge products and an overall mechanism governing phase formation at MnO2 in sulfolane and anhydrous DMSO with and without PVDF binder is presented. This work highlights the importance of careful consideration of electrolyte-cathode material-discharge product interactions in the search for more stable Li-O2 systems. PMID:25640321

  19. Synthesis of NASICON-type structured NaTi2(PO4)3-graphene nanocomposite as an anode for aqueous rechargeable Na-ion batteries.

    PubMed

    Pang, Gang; Yuan, Changzhou; Nie, Ping; Ding, Bing; Zhu, Jiajia; Zhang, Xiaogang

    2014-06-21

    A new solvothermal strategy combined with calcination has been developed to synthesize NaTi2(PO4)3-graphene nanocomposites. X-ray diffraction, thermogravimetric analysis, field-emission scanning electron microscopy and transmission electron microscopy were performed to characterize their microstructures and morphologies. It was found that NASICON-type structured NaTi2(PO4)3 nanoparticles with highly crystallinity were homogeneously anchored on the surface of conducting graphene nanosheets, forming a two-dimensional hybrid nanoarchitecture. A possible growth mechanism was also discussed based on time-dependent experiments. When used as anode materials for Na-ion batteries, the nanocomposites exhibited excellent electrochemical performance with high-rate capability and excellent cycling stability in 1 M Na2SO4 aqueous electrolyte. The electrode delivered high specific capacities of 110, 85, 65, 40 mA h g(-1) at 2, 5, 10 and 20 C, respectively, and still retained 90% of the initial capacity after 100 cycles at 2 C. PMID:24755904

  20. Inter-relationships of MnO 2 precipitation, siderophore-Mn (III) complex formation, siderophore degradation, and iron limitation in Mn (II)-oxidizing bacterial cultures

    NASA Astrophysics Data System (ADS)

    Parker, Dorothy L.; Morita, Takami; Mozafarzadeh, Mylene L.; Verity, Rebecca; McCarthy, James K.; Tebo, Bradley M.

    2007-12-01

    To examine the pathways that form Mn (III) and Mn (IV) in the Mn (II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn (IV)O 2 formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn (III) complex or insoluble Mn (IV)O 2 minerals - but not both simultaneously. PVD-Mn (III) was present, and MnO 2 precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn (III) arose by predominantly ligand-mediated air oxidation of Mn (II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn (III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn (III), a process linked to the production of both MnO 2 and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn (III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO 2 to appear. These results suggest that P. putida cultures produce soluble Mn (III) or MnO 2 by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO 2 under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn (III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn (III) versus MnO 2) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.

  1. Asymmetric Supercapacitors with Dominant Pseudocapacitance in Neutral Aqueous Electrolyte

    NASA Astrophysics Data System (ADS)

    Mao, Yuanbing; Li, Qiang

    2015-03-01

    Electrochemical capacitors (ECs) are promising power sources for portable electronics and hybrid electric vehicles. To solve the poor ionic conductivity, intrinsic inflammability and toxicity issues of current ECs incorporating organic electrolytes, aqueous electrolyte-based asymmetric supercapacitors (ASCs) have been attracting intensive attention recently. In this presentation, prototype MnO2-NFs//KCl//CNTs supercapacitor cells in neutral aqueous electrolyte allow rapid charge/discharge kinetics, fast ionic response, and evident pseudocapacitive dominance due to the unique MnO2-NF architecture and novel ASC design. For the first time, the respective contributions of the pseudocapacitance and EDL capacitance to the overall electrochemical performance of ASCs were differentiated with a proof of pseudocapacitive dominance (qpseudo/qdl = 2.5). To sum, this study provides a brilliant proof-of-concept design of novel supercapacitors with pseudocapacitive dominance to achieve ultimate energy storage applications with both high energy and power density.

  2. Hydrothermal MnO 2: synthesis, structure, morphology and discharge performance

    NASA Astrophysics Data System (ADS)

    Walanda, Daud K.; Lawrance, Geoffrey A.; Donne, Scott W.

    Digestion of Mn 2O 3 in a range of H 2SO 4 solutions (0.01-0 M), at a variety of temperatures (20-140 °C) has led to the formation of a series of kinetically stable manganese dioxide samples via a dissolution-precipitation mechanism that involves disproportionation of a soluble Mn(III) intermediate. The resultant manganese dioxide samples are characterized in terms of their domain of phase stability, chemical composition, structure, morphology and electrochemical performance. γ-MnO 2 predominates at all but high H 2SO 4 concentrations (>5 M), where α-MnO 2 is formed, and high temperatures (>80 °C) where β-MnO 2 is formed. The structural variety of γ-MnO 2 in this domain of stability is interpreted in terms of: (i) the fraction of De Wolff defects ( Pr), which is found to increase as the H 2SO 4 concentration is decreased and the temperature is increased; (ii) microtwinning ( Tw), which despite being less statistically significant, is found to follow a similar trend; (iii) the cation vacancy fraction; (iv) the Mn(III) fraction. Both the latter structural properties decrease as the temperature is increased; but decreasing the H 2SO 4 concentration leads to a decrease in cation vacancy fraction and an increase in Mn(III) fraction. These structural characteristics, in particular the De Wolff defects, are interpreted on a molecular level in terms of soluble Mn(III) intermediate condensation, in which the electrolyte conditions determine the relative proportions of equatorial-axial edge sharing (ramsdellite domains only), and equatorial-axial corner sharing (both ramsdellite and pyrolusite domains) that occurs. Morphological differentiation is easily established due to the different characteristics of each phase. γ-MnO 2 exists as fine needles (250 nm × 50 nm), β-MnO 2 is formed as much larger columns (1 μm × 100 nm), while α-MnO 2 is present as small spheres of up to 400 nm in diameter. Electrochemical characterization by voltammetry in an aqueous 9 M KOH

  3. A consistent model for surface complexation on birnessite (-MnO2) and its application to a column experiment

    NASA Astrophysics Data System (ADS)

    Appelo, C. A. J.; Postma, D.

    1999-10-01

    Available surface complexation models for birnessite required the inclusion of bidentate bonds or the adsorption of cation-hydroxy complexes to account for experimentally observed H+/Mm+ exchange. These models contain inconsistencies and therefore the surface complexation on birnessite was re-examined. Structural data on birnessite indicate that sorption sites are located on three oxygens around a vacancy in the octahedral layer. The three oxygens together carry a charge of -2, i.e., constitute a doubly charged sorption site. Therefore a new surface complexation model was formulated using a doubly charged, diprotic, sorption site where divalent cations adsorbing via inner-sphere complexes bind to the three oxygens. Using the diprotic site concept we have remodeled the experimental data for sorption on birnessite by Murray (1975) using the surface complexation model of Dzombak and Morel (1990). Intrinsic constants for the surface complexation model were obtained with the non-linear optimization program PEST in combination with a modified version of PHREEQC (Parkhurst, 1995). The optimized model was subsequently tested against independent data sets for synthetic birnessite by Balistrieri and Murray (1982) and Wang et al. (1996). It was found to describe the experimental data well. Finally the model was tested against the results of column experiments where cations adsorbed on natural MnO2 coated sand. In this case as well, the diprotic surface complexation model gave an excellent description of the experimental results.

  4. Stretchable Wire-Shaped Asymmetric Supercapacitors Based on Pristine and MnO2 Coated Carbon Nanotube Fibers.

    PubMed

    Xu, Ping; Wei, Bingqing; Cao, Zeyuan; Zheng, Jie; Gong, Ke; Li, Faxue; Yu, Jianyong; Li, Qingwen; Lu, Weibang; Byun, Joon-Hyung; Kim, Byung-Sun; Yan, Yushan; Chou, Tsu-Wei

    2015-06-23

    While the emerging wire-shaped supercapacitors (WSS) have been demonstrated as promising energy storage devices to be implemented in smart textiles, challenges in achieving the combination of both high mechanical stretchability and excellent electrochemical performance still exist. Here, an asymmetric configuration is applied to the WSS, extending the potential window from 0.8 to 1.5 V, achieving tripled energy density and doubled power density compared to its asymmetric counterpart while accomplishing stretchability of up to 100% through the prestrainning-then-buckling approach. The stretchable asymmetric WSS constituted of MnO2/CNT hybrid fiber positive electrode, aerogel CNT fiber negative electrode and KOH-PVA electrolyte possesses a high specific capacitance of around 157.53 μF cm(-1) at 50 mV s(-1) and a high energy density varying from 17.26 to 46.59 nWh cm(-1) with the corresponding power density changing from 7.63 to 61.55 μW cm(-1). Remarkably, a cyclic tensile strain of up to 100% exerts negligible effects on the electrochemical performance of the stretchable asymmetric WSS. Moreover, after 10,000 galvanostatic charge-discharge cycles, the specific capacitance retains over 99%, demonstrating a long cyclic stability. PMID:25961131

  5. Low-temperature molar heat capacities and entropies of MnO2 (pyrolusite), Mn3O4 (hausmanite), and Mn2O3 (bixbyite)

    USGS Publications Warehouse

    Robie, R.A.; Hemingway, B.S.

    1985-01-01

    Pyrolusite (MnO2), hausmanite (Mn3O4), and bixbyite (Mn2O3), are important ore minerals of manganese and accurate values for their thermodynamic properties are desirable to understand better the {p(O2), T} conditions of their formation. To provide accurate values for the entropies of these important manganese minerals, we have measured their heat capacities between approximately 5 and 380 K using a fully automatic adiabatically-shielded calorimeter. All three minerals are paramagnetic above 100 K and become antiferromagnetic or ferrimagnetic at lower temperatures. This transition is expressed by a sharp ??-type anomaly in Cpmo for each compound with Ne??el temperatures TN of (92.2??0.2), (43.1??0.2), and (79.45??0.05) K for MnO2, Mn3O4, and Mn2O3, respectively. In addition, at T ??? 308 K, Mn2O3 undergoes a crystallographic transition, from orthorhombic (at low temperatures) to cubic. A significant thermal effect is associated with this change. Hausmanite is ferrimagnetic below TN and in addition to the normal ??-shape of the heat-capacity maxima in MnO2 and Mn2O3, it has a second rounded maximum at 40.5 K. The origin of this subsidiary bump in the heat capacity is unknown but may be related to a similar "anomalous bump" in the curve of magnetization against temperature at about 39 K observed by Dwight and Menyuk.(1) At 298.15 K the standard molar entropies of MnO2, Mn3O4, and Mn2O3, are (52.75??0.07), (164.1??0.2), and (113.7??0.2) J??K-1??mol-1, respectively. Our value for Mn3O4 is greater than that adopted in the National Bureau of Standards tables(2) by 14 per cent. ?? 1985.

  6. Real-time tracking of hydrogen peroxide secreted by live cells using MnO2 nanoparticles intercalated layered doubled hydroxide nanohybrids.

    PubMed

    Asif, Muhammad; Aziz, Ayesha; Dao, Anh Quang; Hakeem, Abdul; Wang, Haitao; Dong, Shuang; Zhang, Guoan; Xiao, Fei; Liu, Hongfang

    2015-10-22

    We report a facile and green method for the fabrication of new type of electrocatalysts based on MnO2 nanoparticles incorporated on MgAl LDH P-type semiconductive channel and explore its practical applications as high-performance electrode materials for electrochemical biosensor. A series of MgAl layered doubled hydroxide (LDH) nanohybrids with fixed Mg/Al (M(2+)/M(3+) atomic ratio of 3) and varied amount of MnCl2.4H2O are fabricated by a facile co-precipitation method. This approach demonstrates the combination of distinct properties including excellent intercalation features of LDH for entrapping nanoparticles and high loading of MnO2 nanoparticles in the host layers of LDH. Among all samples, Mn5-MgAl with 0.04% loaded manganese has a good crystalline morphology. A well-dispersed MnO2 nanoparticles encapsulated into the host matrix of hydrotalcite exhibit enhanced electrocatalytic activity towards the reduction of H2O2 as well as excellent stability, selectivity and reproducibility due to synergistic effect of good catalytic ability of MnO2 and conductive MgAl LDH. Glass carbon electrode (GCE) modified with Mn5-MgAl possesses a wide linear range of 0.05-78 mM, lowest detection limit 5 μM (S/N = 3) and detection sensitivity of 0.9352 μAmM(-1). This outstanding performance enables it to be used for real-time tracking of H2O2 secreted by live HeLa cells. This work may provide new insight in clinical diagnosis, on-site environmental analysis and point of care testing devices. PMID:26526908

  7. Multifunctional MnO2 nanosheet-modified Fe3O4@SiO2/NaYF4:Yb, Er nanocomposites as novel drug carriers.

    PubMed

    Zhao, Peng; Zhu, Yihua; Yang, Xiaoling; Shen, Jianhua; Jiang, Xin; Zong, Jie; Li, Chunzhong

    2014-01-14

    We report on a novel drug carrier which is based on the combination of magnetic and upconversion (UC) emission of Fe3O4@SiO2/NaYF4:Yb, Er (MSU) hybrids modified with MnO2 nanosheets (MSU/MnO2). The MSU hybrids were fabricated by covalently linking amino-modified Fe3O4@SiO2 particles with carboxyl-functionalized NaYF4:Yb, Er particles. The Fe3O4 core and the NaYF4:Yb, Er shell functioned successfully for magnetic targeting and fluorescence imaging, respectively. MnO2 nanosheets served as drug carriers and UC luminescence quenchers. The drug can be released by introducing glutathione (GSH) which reduces MnO2 to Mn(2+), and at the same time, UC luminescence can be turned on. These results clearly show that these MSU/MnO2 nanocomposites are promising platforms which can be applied to construct a smart drug delivery system with magnetic targeting and GSH-stimulation, as well as tracking by UC luminescence. PMID:24065169

  8. 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.

  9. Enhanced simultaneous detection of ractopamine and salbutamol--Via electrochemical-facial deposition of MnO2 nanoflowers onto 3D RGO/Ni foam templates.

    PubMed

    Wang, Ming Yan; Zhu, Wei; Ma, Lin; Ma, Juan Juan; Zhang, Dong En; Tong, Zhi Wei; Chen, Jun

    2016-04-15

    In this paper, we report a facile method to successfully fabricate MnO2 nanoflowers loaded onto 3D RGO@nickel foam, showing enhanced biosensing activity due to the improved structural integration of different electrode materials components. When the as-prepared 3D hybrid electrodes were investigated as a binder-free biosensor, two well-defined and separate differential pulse voltammetric peaks for ractopamine (RAC) and salbutamol (SAL) were observed, indicating the simultaneous selective detection of both β-agonists possible. The MnO2/RGO@NF sensor also demonstrated a linear relationship over a wide concentration range of 17 nM to 962 nM (R=0.9997) for RAC and 42 nM to 1463 nM (R=0.9996) for SAL, with the detection limits of 11.6 nM for RAC and 23.0 nM for SAL. In addition, the developed MnO2/RGO@NF sensor was further investigated to detect RAC and SAL in pork samples, showing satisfied comparable results in comparison with analytic results from HPLC. PMID:26623510

  10. Formation of hierarchical CoMoO4@MnO2 core-shell nanosheet arrays on nickel foam with markedly enhanced pseudocapacitive properties

    NASA Astrophysics Data System (ADS)

    Zhang, Ziqing; Bao, Fuxi; Zhang, Yingnan; Feng, Likun; Ji, Ying; Zhang, Hongdan; Sun, Qiushi; Feng, Shouhua; Zhao, Xudong; Liu, Xiaoyang

    2015-11-01

    In this work, the hierarchical CoMoO4@MnO2 core-shell nanosheet arrays have been synthesized, which are grown directly on Ni foam as an integrated electrode for supercapacitors. Nanosheet arrays of cobalt-molybdenum precursors are synthesized first by a mild hydrothermal reaction and used as the "core". After the second facile hydrothermal process with a successive annealing, the Co-Mo precursors are transformed into the 3D hierarchical CoMoO4@MnO2 core-shell nanostructure. This core-shell heterostructure exhibits desirable electrochemical properties. It shows a high specific capacitance of 2159.4 F g-1 (2.27 F cm-2) at 3 mA cm-2 and high cycle stability with 93% retention of its initial specific capacitance at 20 mA cm-2 after 3000 cycles in 1 M KOH solution. In conclusion, the CoMoO4@MnO2 composites could be used as promising electrode materials for electrochemical energy storage due to their remarkable electrochemical properties.

  11. In-situ synthesis of MnO2@CNT microsphere composites with enhanced electrochemical performances for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Mao, Wenfeng; Ai, Guo; Dai, Yiling; Fu, Yanbao; Ma, Ye; Shi, Shouwen; Soe, Ryan; Zhang, Xinhe; Qu, Deyang; Tang, Zhiyuan; Battaglia, Vincent S.

    2016-04-01

    An inner coating method is developed to synthesize electrode materials for lithium ion batteries. Different from other conventional coating methods, the inner coating method employs one-dimensional (1D) conductive materials to form a three-dimensional (3D) electronic conductive and mechanical network, which can not only improve electronic and ionic conductivity, increase the reactive area, but it also accommodates volume changes associated with active materials. The concept of our inner coating method is demonstrated via the synthesis of MnO2@CNT microspheres, which uses CNT as the inner coating material. The reversible capacity increases significantly from 528.0 mAh g-1 for the MnO2 (without inner coating) to 1097.3 mAh g-1 for the MnO2@CNT (with inner coating). Cycling stability is also greatly improved via inner coating technique. This method can be extended to the synthesis of other high capacity electrode materials, which will promote the development of next-generation lithium-ion batteries.

  12. Polyethylenimine-Mediated Electrostatic Assembly of MnO2 Nanorods on Graphene Oxides for Use as Anodes in Lithium-Ion Batteries.

    PubMed

    Chae, Changju; Kim, Ki Woong; Yun, Young Jun; Lee, Daehee; Moon, Jooho; Choi, Youngmin; Lee, Sun Sook; Choi, Sungho; Jeong, Sunho

    2016-05-11

    In recent years, the development of electrochemically active materials with excellent lithium storage capacity has attracted tremendous attention for application in high-performance lithium-ion batteries. MnO2-based composite materials have been recognized as one of promising candidates owing to their high theoretical capacity and cost-effectiveness. In this study, a previously unrecognized chemical method is proposed to induce intra-stacked assembly from MnO2 nanorods and graphene oxide (GO), which is incorporated as an electrically conductive medium and a structural template, through polyethylenimine (PEI)-derived electrostatic modulation between both constituent materials. It is revealed that PEI, a cationic polyelectrolyte, is capable of effectively forming hierarchical, two-dimensional MnO2-RGO composites, enabling highly reversible capacities of 880, 770, 630, and 460 mA·h/g at current densities of 0.1, 1, 3, and 5 A/g, respectively. The role of PEI in electrostatically assembled composite materials is clarified through electrochemical impedance spectroscopy-based comparative analysis. PMID:27082880

  13. Three-Dimensional Ordered Mesoporous MnO2-Supported Ag Nanoparticles for Catalytic Removal of Formaldehyde.

    PubMed

    Bai, Bingyang; Qiao, Qi; Arandiyan, Hamidreza; Li, Junhua; Hao, Jiming

    2016-03-01

    Three-dimensional (3D) ordered mesoporous Ag/MnO2 catalyst was prepared by impregnation method based on 3D-MnO2 and used for catalytic oxidation of HCHO. Ag nanoparticles are uniformly distributed on the polycrystalline wall of 3D-MnO2. The addition of Ag does not change the 3D ordered mesoporous structure of the Ag/MnO2, but does reduce the pore size and surface area. Ag nanoparticles provide sufficient active site for the oxidation reaction of HCHO, and Ag (111) crystal facets in the Ag/MnO2 are active faces. The 8.9% Ag/MnO2 catalyst shows a higher normalized rate (10.1 nmol·s(-1)·m(-2) at 110 °C) and TOF (0.007 s(-1) at 110 °C) under 1300 ppm of HCHO and 150 000 h(-1) of GHSV, and its apparent activation energy of the reaction is the lowest (39.1 kJ/mol). More Ag active sites, higher low-temperature reducibility, more abundant surface lattice oxygen species, oxygen vacancies, and lattice defects generated from interaction Ag with MnO2 are responsible for the excellent catalytic performance of HCHO oxidation on the 8.9% Ag/MnO2 catalyst. The 8.9% Ag/MnO2 catalyst remained highly active and stable under space velocity increasing from 60 000 to 150 000 h(-1), under initial HCHO concentration increasing from 500 to 1300 ppm, and under the presence of humidity, respectively. PMID:26629972

  14. Appendix C: Recharge

    SciTech Connect

    Fayer, Michael J.; Keller, Jason M.

    2008-01-17

    This appendix provides estimates of recharge rates for the soil and vegetation conditions in and around the single-shell tank (SST) waste management areas (WMAs). The purpose is to combine published data with recent information to provide the most current recharge estimates. Recharge rates were estimated for areas that remain natural and undisturbed, areas where the vegetation has been disturbed, areas where both the vegetation and the soil have been disturbed, and areas that are engineered (e.g., surface barrier). Methods used include lysimetry, tracers, and simuations. This appendix summarizes the information in the recharge data package for the SST Waste Management Areas), which builds upon previous reports on the Hanford vadose zone data and Integrated Disposal Facility recharge with information available after those reports were published, including field measurements and simulations using weather data through 2006.

  15. The Exxon rechargeable cells. [solar rechargeable clocks

    NASA Technical Reports Server (NTRS)

    Malachesky, P. A.

    1980-01-01

    The design and performance of ambient temperature secondary cells based on the titanium disulfide cathode are discussed. These limited performance products were developed for microelectronic applications such as solar rechargeable watches and clocks which require low drain rate and do not require many deep cycles.

  16. Rechargeability and economic aspects of alkaline zinc-manganese dioxide cells for electrical storage and load leveling

    NASA Astrophysics Data System (ADS)

    Ingale, Nilesh D.; Gallaway, Joshua W.; Nyce, Michael; Couzis, Alexander; Banerjee, Sanjoy

    2015-02-01

    Batteries based on manganese dioxide (MnO2) cathodes are good candidates for grid-scale electrical energy storage, as MnO2 is low-cost, relatively energy dense, safe, water-compatible, and non-toxic. Alkaline Zn-MnO2 cells, if cycled at reduced depth of discharge (DOD), have been found to achieve substantial cycle life with battery costs projected to be in the range of 100 to 150 per kWh (delivered). Commercialization of rechargeable Zn-MnO2 batteries has in the past been hampered due to poor cycle life. In view of this, the work reported here focuses on the long-term rechargeability of prismatic MnO2 cathodes at reduced DOD when exposed to the effects of Zn anodes and with no additives or specialty materials. Over 3000 cycles is shown to be obtainable at 10% DOD with energy efficiency >80%. The causes of capacity fade during long-term cycling are also investigated and appear to be mainly due to the formation of irreversible manganese oxides in the cathode. Analysis of the data indicates that capacity loss is rapid in the first 250 cycles, followed by a regime of stability that can last for thousands of cycles. A model has been developed that captures the behavior of the cells investigated using measured state of charge (SOC) data as input. An approximate economic analysis is also presented to evaluate the economic viability of Zn-MnO2 batteries based on the experiments reported here.

  17. Rechargeability and economic aspects of alkaline zinc-manganese dioxide cells for electrical storage and load leveling

    SciTech Connect

    Ingale, ND; Gallaway, JW; Nyce, M; Couzis, A; Banerjee, S

    2015-02-15

    Batteries based on manganese dioxide (MnO2) cathodes are good candidates for grid-scale electrical energy storage, as MnO2 is low-cost, relatively energy dense, safe, water-compatible, and non-toxic. Alkaline Zn-MnO2 cells, if cycled at reduced depth of discharge (DOD), have been found to achieve substantial cycle life with battery costs projected to be in the range of $100 to 150 per kWh (delivered). Commercialization of rechargeable Zn-MnO2 batteries has in the past been hampered due to poor cycle life. In view of this, the work reported here focuses on the long-term rechargeability of prismatic MnO2 cathodes at reduced DOD when exposed to the effects of Zn anodes and with no additives or specialty materials. Over 3000 cycles is shown to be obtainable at 10% DOD with energy efficiency >80%. The causes of capacity fade during long-term cycling are also investigated and appear to be mainly due to the formation of irreversible manganese oxides in the cathode. Analysis of the data indicates that capacity loss is rapid in the first 250 cycles, followed by a regime of stability that can last for thousands of cycles. A model has been developed that captures the behavior of the cells investigated using measured state of charge (SOC) data as input. An approximate economic analysis is also presented to evaluate the economic viability of Zn-MnO2 batteries based on the experiments reported here. (C) 2014 Elsevier B.V. All rights reserved.

  18. Nanostructured porous RuO2/MnO2 as a highly efficient catalyst for high-rate Li-O2 batteries.

    PubMed

    Wang, Guoqing; Huang, Liliang; Huang, Wei; Xie, Jian; Du, Gaohui; Zhang, Shichao; Zhu, Peiyi; Cao, Gaoshao; Zhao, Xinbing

    2015-12-28

    Despite the recent advancements in Li-O(2) (or Li-air) batteries, great challenges still remain to realize high-rate, long-term cycling. In this work, a binder-free, nanostructured RuO(2)/MnO(2) catalytic cathode was designed to realize the operation of Li-O(2) batteries at high rates. At a current density as high as 3200 mA g(-1) (or ∼1.3 mA cm(-2)), the RuO(2)/MnO(2) catalyzed Li-O(2) batteries with LiI can sustain stable cycling of 170 and 800 times at limited capacities of 1000 and 500 mA h g(-1), respectively, with low charge cutoff potentials of ∼4.0 and <3.8 V, respectively. The underlying mechanism of the high catalytic performance of MnO(2)/RuO(2) was also clarified in this work. It was found that with the catalytic effect of RuO(2), Li(2)O(2) can crystallize into a thin-sheet form and realize a conformal growth on sheet-like δ-MnO(2) at a current density up to 3200 mA g(-1), constructing a sheet-on-sheet structure. This crystallization behavior of Li(2)O(2) not only defers the electrode passivation upon discharge but also renders easy decomposition of Li(2)O(2) upon charge, leading to low polarizations and reduced side reactions. This work provides a unique design of catalytic cathodes capable of controlling Li(2)O(2) growth and sheds light on the design of high-rate, long-life Li-O(2) batteries with potential applications in electric vehicles. PMID:26592423

  19. Na0.44MnO2 with very fast sodium diffusion and stable cycling synthesized via polyvinylpyrrolidone-combustion method

    NASA Astrophysics Data System (ADS)

    Dai, Kehua; Mao, Jing; Song, Xiangyun; Battaglia, Vince; Liu, Gao

    2015-07-01

    Na0.44MnO2 is a very promising cathode material in sodium-ion batteries for large-scale application. Na0.44MnO2 with very fast sodium diffusion and stable cycling is prepared by polyvinylpyrrolidone (PVP)-combustion method. X-ray diffraction, scanning electron microscope and high-resolution transmission electron microscopy are conducted to explore the morphology and structure. Electrochemical performance of the samples is examined in coin cells with sodium foil anode and nonaqueous electrolyte. The Na0.44MnO2 sample synthesized at 900 °C (NMO-900) discharges the highest capacity of 122.9 mAh g-1 at C/5. A fast-rate-test technique developed by Newman et al. is adopted for quick determination of the rate capability. All the samples exhibit good rate capability while the NMO-900 shows the best. Normal rate test result supports the reliability of the fast rate test. Even at 20C charge and discharge rate, the NMO-900 delivers 99 mAh g-1 capacity. The chemical diffusion coefficient of sodium is measured to be around 3 × 10-12 cm2 s-1 by potential intermittent titration technique (PITT). The cycling stability is also very good. The capacity retention after 100 cycles at 1C is 87.9% and the capacity still remains 82.9% even after 700 cycles at 10C. During cycling the coulombic efficiency keeps near 99.8%.

  20. Electrospun lignin-derived carbon nanofiber mats surface-decorated with MnO2 nanowhiskers as binder-free supercapacitor electrodes with high performance

    NASA Astrophysics Data System (ADS)

    Ma, Xiaojing; Kolla, Praveen; Zhao, Yong; Smirnova, Alevtina L.; Fong, Hao

    2016-09-01

    The aim of this study is to explore innovative materials for the development of next-generation supercapacitor electrodes. The hypothesis is that, upon the surface-decoration with appropriate amount of MnO2 nanowhiskers, freestanding and highly graphitic electrospun carbon nanofiber (ECNF) mats (with fiber diameters of ∼200 nm and BET specific surface areas of ∼583 m2 g-1) derived from a natural product of lignin would be binder-free supercapacitor electrodes with high performance. To test the hypothesis, the ECNF mats have been prepared first; thereafter, the acquired ECNF mats have been surface-decorated with varied amounts of MnO2 nanowhiskers to prepare three types of ECNF/MnO2 mats. The morphological and structural properties of ECNF and ECNF/MnO2 mats are characterized by SEM, TEM and XRD, the weight percentages of MnO2 nanowhiskers in three ECNF/MnO2 mats are determined by thermal gravimetric analysis; while the electrochemical performance of each mat/electrode is evaluated by cyclic voltammetry, galvanostatic charge/discharge method, and electrochemical impedance spectroscopy. This study reveals that, all of the three ECNF/MnO2 mats/electrodes have significantly enhanced electrochemical performances compared to the ECNF mat/electrode; while the ECNF/MnO2 (1:1) mat/electrode exhibits the highest gravimetric capacitance of 83.3 F g-1, energy density of 84.3 W h kg-1, and power density of 5.72 kW kg-1.

  1. Multidimensional MnO2 nanohair-decorated hybrid multichannel carbon nanofiber as an electrode material for high-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Jun, Jaemoon; Lee, Jun Seop; Shin, Dong Hoon; Kim, Sung Gun; Jang, Jyongsik

    2015-09-01

    One-dimensional (1D)-structured nanomaterials represent one of the most attractive candidates for energy-storage systems due to their contribution to design simplicity, fast charge-transportation network, and their allowance for more accessible ion diffusion. In particular, 1D-structured nanomaterials with a highly complex inner-pore configuration enhance functionality by taking advantage of both the hollow and 1D structures. In this study, we report a MnO2 nanohair-decorated, hybrid multichannel carbon nanofiber (Mn_MCNF) fabricated via single-nozzle co-electrospinning of two immiscible polymer solutions, followed by carbonization and redox reactions. With improved ion accessibility, the optimized Mn_MCNF sample (Mn_MCNF_60 corresponding to a reaction duration time of 60 min for optimal MnO2 nanohair growth) exhibited a high specific capacitance of 855 F g-1 and excellent cycling performance with ~87.3% capacitance retention over 5000 cycles.One-dimensional (1D)-structured nanomaterials represent one of the most attractive candidates for energy-storage systems due to their contribution to design simplicity, fast charge-transportation network, and their allowance for more accessible ion diffusion. In particular, 1D-structured nanomaterials with a highly complex inner-pore configuration enhance functionality by taking advantage of both the hollow and 1D structures. In this study, we report a MnO2 nanohair-decorated, hybrid multichannel carbon nanofiber (Mn_MCNF) fabricated via single-nozzle co-electrospinning of two immiscible polymer solutions, followed by carbonization and redox reactions. With improved ion accessibility, the optimized Mn_MCNF sample (Mn_MCNF_60 corresponding to a reaction duration time of 60 min for optimal MnO2 nanohair growth) exhibited a high specific capacitance of 855 F g-1 and excellent cycling performance with ~87.3% capacitance retention over 5000 cycles. Electronic supplementary information (ESI) available: Experimental data includes optical images, TGA, magnified pore distribution curves and supercapacitor device of the MCNF and Mn_MCNF. See DOI: 10.1039/C5NR03616J

  2. Intrinsic quantum spin Hall and anomalous Hall effects in h-Sb/Bi epitaxial growth on a ferromagnetic MnO2 thin film

    NASA Astrophysics Data System (ADS)

    Zhou, Jian; Sun, Qiang; Wang, Qian; Kawazoe, Yoshiyuki; Jena, Puru

    2016-05-01

    Exploring a two-dimensional intrinsic quantum spin Hall state with a large band gap as well as an anomalous Hall state in realizable materials is one of the most fundamental and important goals for future applications in spintronics, valleytronics, and quantum computing. Here, by combining first-principles calculations with a tight-binding model, we predict that Sb or Bi can epitaxially grow on a stable and ferromagnetic MnO2 thin film substrate, forming a flat honeycomb sheet. The flatness of Sb or Bi provides an opportunity for the existence of Dirac points in the Brillouin zone, with its position effectively tuned by surface hydrogenation. The Dirac points in spin up and spin down channels split due to the proximity effects induced by MnO2. In the presence of both intrinsic and Rashba spin-orbit coupling, we find two band gaps exhibiting a large band gap quantum spin Hall state and a nearly quantized anomalous Hall state which can be tuned by adjusting the Fermi level. Our findings provide an efficient way to realize both quantized intrinsic spin Hall conductivity and anomalous Hall conductivity in a single material.Exploring a two-dimensional intrinsic quantum spin Hall state with a large band gap as well as an anomalous Hall state in realizable materials is one of the most fundamental and important goals for future applications in spintronics, valleytronics, and quantum computing. Here, by combining first-principles calculations with a tight-binding model, we predict that Sb or Bi can epitaxially grow on a stable and ferromagnetic MnO2 thin film substrate, forming a flat honeycomb sheet. The flatness of Sb or Bi provides an opportunity for the existence of Dirac points in the Brillouin zone, with its position effectively tuned by surface hydrogenation. The Dirac points in spin up and spin down channels split due to the proximity effects induced by MnO2. In the presence of both intrinsic and Rashba spin-orbit coupling, we find two band gaps exhibiting a large band gap quantum spin Hall state and a nearly quantized anomalous Hall state which can be tuned by adjusting the Fermi level. Our findings provide an efficient way to realize both quantized intrinsic spin Hall conductivity and anomalous Hall conductivity in a single material. Electronic supplementary information (ESI) available: Band structure of h-Sb@MnO2 and h-Bi@MnO2, formation energy variation with respect to absorbing H atoms, tight binding band dispersion, and (spin) Berry Hall curvature of the conductance band. See DOI: 10.1039/c6nr01949h

  3. Estimating groundwater recharge

    USGS Publications Warehouse

    Stonestrom, David A.

    2011-01-01

    Groundwater recharge is the entry of fresh water into the saturated portion of the subsurface part of the hydrologic cycle, the modifier "saturated" indicating that the pressure of the pore water is greater than atmospheric.

  4. Nanocomposite of Fe2 O3 @C@MnO2 as an Efficient Cathode Catalyst for Rechargeable Lithium-Oxygen Batteries.

    PubMed

    Hu, Xiaofei; Cheng, Fangyi; Zhang, Ning; Han, Xiaopeng; Chen, Jun

    2015-11-01

    A new design and synthesis of Fe2O3 @C@MnO2 nanocomposite via aerosol spray pyrolysis and electrodeposition is reported for application in rechargeable Li-O2 batteries. Owing to the superior oxygen reduction/evolution reaction bifunctional catalytic activities attributed to the combined function of Fe2O3 and MnO2 and facile charge transfer in the carbon matrix, the nanocomposite exhibits long life, large capacity, and a small overpotential in Li-O2 batteries. PMID:26313469

  5. Aqueous manganese dioxide ink for paper-based capacitive energy storage devices.

    PubMed

    Qian, Jiasheng; Jin, Huanyu; Chen, Bolei; Lin, Mei; Lu, Wei; Tang, Wing Man; Xiong, Wei; Chan, Lai Wa Helen; Lau, Shu Ping; Yuan, Jikang

    2015-06-01

    We report a simple approach based on a chemical reduction method to synthesize aqueous inorganic ink comprised of hexagonal MnO2 nanosheets. The MnO2 ink exhibits long-term stability and continuous thin films can be formed on various substrates without using any binder. To obtain a flexible electrode for capacitive energy storage, the MnO2 ink was printed onto commercially available A4 paper pretreated with multiwalled carbon nanotubes. The electrode exhibited a maximum specific capacitance of 1035 F g(-1) (91.7 mF cm(-2)). Paper-based symmetric and asymmetric capacitors were assembled, which gave a maximum specific energy density of 25.3 Wh kg(-1) and a power density of 81 kW kg(-1). The device could maintain a 98.9% capacitance retention over 10 000 cycles at 4 A g(-1). The MnO2 ink could be a versatile candidate for large-scale production of flexible and printable electronic devices for energy storage and conversion. PMID:25891235

  6. Effects of Electrodeposition Mode and Deposition Cycle on the Electrochemical Performance of MnO2-NiO Composite Electrodes for High-Energy-Density Supercapacitors

    PubMed Central

    Rusi; Majid, S. R.

    2016-01-01

    Nanostructured network-like MnO2-NiO composite electrodes were electrodeposited onto stainless steel substrates via different electrodeposition modes, such as chronopotentiometry, chronoamperometry, and cyclic voltammetry, and then subjected to heat treatment at 300°C for metal oxide conversion. X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy were used to study the crystalline natures and morphologies of the deposited films. The electrochemical properties were investigated using cyclic voltammetry and charge/discharge tests. The results revealed that the electrochemical performance of the as-obtained composite electrodes depended on the electrodeposition mode. The electrochemical properties of MnO2-NiO composite electrodes prepared using cyclic voltammetry exhibited the highest capacitance values and were most influenced by the deposition cycle number. The optimum specific capacitance was 3509 Fg−1 with energy and power densities of 1322 Wh kg−1 and 110.5 kW kg−1, respectively, at a current density of 20 Ag−1 in a mixed KOH/K3Fe(CN)6 electrolyte. PMID:27182595

  7. Effects of Electrodeposition Mode and Deposition Cycle on the Electrochemical Performance of MnO2-NiO Composite Electrodes for High-Energy-Density Supercapacitors.

    PubMed

    Rusi; Majid, S R

    2016-01-01

    Nanostructured network-like MnO2-NiO composite electrodes were electrodeposited onto stainless steel substrates via different electrodeposition modes, such as chronopotentiometry, chronoamperometry, and cyclic voltammetry, and then subjected to heat treatment at 300°C for metal oxide conversion. X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy were used to study the crystalline natures and morphologies of the deposited films. The electrochemical properties were investigated using cyclic voltammetry and charge/discharge tests. The results revealed that the electrochemical performance of the as-obtained composite electrodes depended on the electrodeposition mode. The electrochemical properties of MnO2-NiO composite electrodes prepared using cyclic voltammetry exhibited the highest capacitance values and were most influenced by the deposition cycle number. The optimum specific capacitance was 3509 Fg-1 with energy and power densities of 1322 Wh kg-1 and 110.5 kW kg-1, respectively, at a current density of 20 Ag-1 in a mixed KOH/K3Fe(CN)6 electrolyte. PMID:27182595

  8. Enhanced Sintering of β"-Al2O3/YSZ with the Sintering Aids of TiO2 and MnO2

    SciTech Connect

    Lu, Xiaochuan; Li, Guosheng; Kim, Jin Yong; Meinhardt, Kerry D.; Sprenkle, Vincent L.

    2015-07-11

    β"-Al2O3 has been the dominated choice for the electrolyte materials of sodium batteries because of its high ionic conductivity, excellent stability with the electrode materials, satisfactory mechanical strength, and low material cost. To achieve adequate electrical and mechanical performance, sintering of β"-Al2O3 is typically carried out at temperatures above 1600oC with deliberate efforts on controlling the phase, composition, and microstructure. Here, we reported a simple method to fabricate β"-Al2O3/YSZ electrolyte at relatively lower temperatures. With the starting material of boehmite, single phase of β"-Al2O3 can be achieved at as low as 1200oC. It was found that TiO2 was extremely effective as a sintering aid for the densification of β"-Al2O3 and similar behavior was observed with MnO2 for YSZ. With the addition of 2 mol% TiO2 and 5 mol% MnO2, the β"-Al2O3/YSZ composite was able to be densified at as low as 1400oC with a fine microstructure and good electrical/mechanical performance. This study demonstrated a new approach of synthesis and sintering of β"-Al2O3/YSZ composite, which represented a simple and low-cost method for fabrication of high-performance β"-Al2O3/YSZ electrolyte.

  9. Intrinsic quantum spin Hall and anomalous Hall effects in h-Sb/Bi epitaxial growth on a ferromagnetic MnO2 thin film.

    PubMed

    Zhou, Jian; Sun, Qiang; Wang, Qian; Kawazoe, Yoshiyuki; Jena, Puru

    2016-06-01

    Exploring a two-dimensional intrinsic quantum spin Hall state with a large band gap as well as an anomalous Hall state in realizable materials is one of the most fundamental and important goals for future applications in spintronics, valleytronics, and quantum computing. Here, by combining first-principles calculations with a tight-binding model, we predict that Sb or Bi can epitaxially grow on a stable and ferromagnetic MnO2 thin film substrate, forming a flat honeycomb sheet. The flatness of Sb or Bi provides an opportunity for the existence of Dirac points in the Brillouin zone, with its position effectively tuned by surface hydrogenation. The Dirac points in spin up and spin down channels split due to the proximity effects induced by MnO2. In the presence of both intrinsic and Rashba spin-orbit coupling, we find two band gaps exhibiting a large band gap quantum spin Hall state and a nearly quantized anomalous Hall state which can be tuned by adjusting the Fermi level. Our findings provide an efficient way to realize both quantized intrinsic spin Hall conductivity and anomalous Hall conductivity in a single material. PMID:27181160

  10. Enhanced sintering of β″-Al2O3/YSZ with the sintering aids of TiO2 and MnO2

    NASA Astrophysics Data System (ADS)

    Lu, Xiaochuan; Li, Guosheng; Kim, Jin Y.; Meinhardt, Kerry D.; Sprenkle, Vincent L.

    2015-11-01

    β″-Al2O3 has been the dominated choice for the electrolyte materials of sodium batteries because of its high ionic conductivity, excellent stability with the electrode materials, satisfactory mechanical strength, and low material cost. To achieve adequate electrical and mechanical performance, sintering of β″-Al2O3 is typically carried out at temperatures above 1600 °C with deliberate efforts on controlling the phase, composition, and microstructure. Here, we reported a simple method to fabricate β″-Al2O3/YSZ electrolyte at relatively lower temperatures. With the starting material of boehmite, single phase of β″-Al2O3 can be achieved at as low as 1200 °C. It was found that TiO2 was extremely effective as a sintering aid for the densification of β″-Al2O3 and similar behavior was observed with MnO2 for YSZ. With the addition of 2 mol% TiO2 and 5 mol% MnO2, the β″-Al2O3/YSZ composite was able to be densified at as low as 1400 °C with a fine microstructure and good electrical/mechanical performance. This study demonstrated a new approach of synthesis and sintering of β″-Al2O3/YSZ composite, which represented a simple and low-cost method for fabrication of high-performance β″-Al2O3/YSZ electrolyte.

  11. High-rate performance electrospun Na0.44MnO2 nanofibers as cathode material for sodium-ion batteries

    NASA Astrophysics Data System (ADS)

    Fu, Bi; Zhou, Xuan; Wang, Yaping

    2016-04-01

    Sodium-ion batteries (SIBs) are considered as one of the most promising candidates to replace lithium-ion batteries (LIBs), because of their similar electrochemical properties, and geographical limitations of lithium. However, searching for the appropriate cathode materials for SIBs that can accommodate structure change during the insertion and extraction of sodium ions is facing great challenges due to the relatively larger size of sodium ion. Na0.44MnO2 has recently attracted significant attention because its crystal structure exhibits two types of large channels formed by MnO6 octahedra and MnO5 square pyramids, which facilitate the transportation of sodium ions. However, suffering from the slow kinetics and structural degradation, its rate performance is still not satisfied. Here, we report the fabrication of two types of Na0.44MnO2 hierarchical structures by optimized electrospinning and controlled subsequent annealing process. One is nanofiber (NF) which demonstrates a superior rate performance with reversible specific capacity of 69.5 mAh g-1 at 10 C, attributed to its one-dimensional (1D) ultralong and continuous fibrous network structure; the other is nanorod (NR) which exhibits an excellent cyclic performance with reversible specific capacity of 120 mAh g-1 after 140 cycles, due to its large S-shaped tunnel structure with a single crystalline structure.

  12. Rechargeability of alkaline Zn-MnO2 batteries: Experimental and mathematical studies

    NASA Astrophysics Data System (ADS)

    Ingale, Nilesh D.

    Batteries based on manganese dioxide (MnO2) cathodes are good candidates for grid-scale electrical energy storage, as MnO2 is low-cost, relatively energy dense, safe, water-compatible, and non-toxic. Alkaline Zn-MnO2 cells, if cycled at reduced depth of discharge (DOD), have been found to achieve substantial cycle life with battery costs projected to be in the range of $100 to 150/kWh (delivered). Commercialization of rechargeable Zn-MnO2 batteries has in the past been hampered due to poor cycle life. In view of this, the work reported here focuses on the long-term rechargeability of prismatic MnO2 cathodes at reduced DOD when exposed to the effects of Zn anodes and with no additives or specialty materials. Over 3000 cycles is shown to be obtainable at 10% DOD with energy efficiency >80%. The causes of capacity fade during long-term cycling are also investigated and appear to be mainly due to the formation of irreversible manganese oxides in the cathode. Analysis of the data indicates that capacity loss is rapid in the first 250 cycles, followed by a regime of stability that can last for thousands of cycles. A model has been developed that captures the behavior of the cells investigated using measured state of charge (SOC) data as input. An approximate economic analysis is also presented to evaluate the economic viability of Zn-MnO2 batteries based on the experiments reported here. The potential of Zn-MnO2 batteries as starting-lighting-ignition (SLI) batteries was also investigated. The impedance contributing parameters at high discharge rates were identified and their effect at high currents was investigated. It was found that prismatic configuration; optimized electrode thickness, electrolyte concentration and electrode size help to achieve high currents for short period of time. In this work, the potential of Zn-MnO 2 batteries for energy as well as power supply has been successfully investigated.

  13. Recharging Batteries Chemically

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Rowlette, J.; Graf, J.

    1985-01-01

    Iron/air batteries recharged chemically by solution of strong base in alcohol or by basic alcohol solution of reducing agent. Although method still experimental, it has potential for batteries in electric automobiles or as energy system in remote applications. Also used in quiet operations where noise or infrared signature of diesel engine is not desired.

  14. Thermal Decomposition Behaviors and Burning Characteristics of AN/RDX-Based Composite Propellants Supplemented with MnO2 and Fe2O3

    NASA Astrophysics Data System (ADS)

    Kohga, Makoto; Naya, Tomoki

    2015-10-01

    Ammonium nitrate (AN)-based composite propellants have gained popularity because of the clean burning nature of AN as an oxidizer. However, such propellants have several disadvantages such as poor ignition and low burning rate. The burning characteristics of the AN propellant were improved when a portion of this propellant was replaced by an energetic material and the addition of a catalyst. In this study, RDX (1,3,5-trinitroperhydro-1,3,5-triazine) was used as the energetic material, and Fe2O3 and MnO2 were used as catalysts. The burning characteristics of the AN/RDX propellants supplemented with catalysts were investigated, and the effects of the replacement of AN by RDX and the catalyst addition were evaluated.

  15. MnO2 Nanosheets Grown on Nitrogen-Doped Hollow Carbon Shells as a High-Performance Electrode for Asymmetric Supercapacitors.

    PubMed

    Li, Lei; Li, Rumin; Gai, Shili; Ding, Shujiang; He, Fei; Zhang, Milin; Yang, Piaoping

    2015-05-01

    A hierarchical hollow hybrid composite, namely, MnO2 nanosheets grown on nitrogen-doped hollow carbon shells (NHCSs@MnO2 ), was synthesized by a facile in situ growth process followed by calcination. The composite has a high surface area (251 m(2) g(-1) ) and mesopores (4.5 nm in diameter), which can efficiently facilitate transport during electrochemical cycling. Owing to the synergistic effect of NHCSs and MnO2 , the composite shows a high specific capacitance of 306 F g(-1) , good rate capability, and an excellent cycling stability of 95.2 % after 5000 cycles at a high current density of 8 A g(-1) . More importantly, an asymmetric supercapacitor (ASC) assembled by using NHCSs@MnO2 and activated carbon as the positive and negative electrodes exhibits high specific capacitance (105.5 F g(-1) at 0.5 A g(-1) and 78.5 F g(-1) at 10 A g(-1) ) with excellent rate capability, achieves a maximum energy density of 43.9 Wh kg(-1) at a power density of 408 W kg(-1) , and has high stability, whereby the ASC retains 81.4 % of its initial capacitance at a current density of 5 A g(-1) after 4000 cycles. Therefore, the NHCSs@MnO2 electrode material is a promising candidate for future energy-storage systems. PMID:25801647

  16. Enhanced resistance to oxidative decomposition of aqueous electrolytes for aqueous lithium-ion batteries.

    PubMed

    Miyazaki, Kohei; Shimada, Toshiki; Ito, Satomi; Yokoyama, Yuko; Fukutsuka, Tomokazu; Abe, Takeshi

    2016-04-11

    An efficient electrolyte solution containing organic sulfonates for use in aqueous rechargeable lithium-ion batteries (ARLBs) is shown to provide a wide potential window and enable a high operating voltage for ARLBs. PMID:26911197

  17. Low-cost flexible supercapacitors with high-energy density based on nanostructured MnO2 and Fe2O3 thin films directly fabricated onto stainless steel

    NASA Astrophysics Data System (ADS)

    Gund, Girish S.; Dubal, Deepak P.; Chodankar, Nilesh R.; Cho, Jun Y.; Gomez-Romero, Pedro; Park, Chan; Lokhande, Chandrakant D.

    2015-07-01

    The facile and economical electrochemical and successive ionic layer adsorption and reaction (SILAR) methods have been employed in order to prepare manganese oxide (MnO2) and iron oxide (Fe2O3) thin films, respectively with the fine optimized nanostructures on highly flexible stainless steel sheet. The symmetric and asymmetric flexible-solid-state supercapacitors (FSS-SCs) of nanostructured (nanosheets for MnO2 and nanoparticles for Fe2O3) electrodes with Na2SO4/Carboxymethyl cellulose (CMC) gel as a separator and electrolyte were assembled. MnO2 as positive and negative electrodes were used to fabricate symmetric SC, while the asymmetric SC was assembled by employing MnO2 as positive and Fe2O3 as negative electrode. Furthermore, the electrochemical features of symmetric and asymmetric SCs are systematically investigated. The results verify that the fabricated symmetric and asymmetric FSS-SCs present excellent reversibility (within the voltage window of 0-1 V and 0-2 V, respectively) and good cycling stability (83 and 91%, respectively for 3000 of CV cycles). Additionally, the asymmetric SC shows maximum specific capacitance of 92 Fg-1, about 2-fold of higher energy density (41.8 Wh kg-1) than symmetric SC and excellent mechanical flexibility. Furthermore, the “real-life” demonstration of fabricated SCs to the panel of SUK confirms that asymmetric SC has 2-fold higher energy density compare to symmetric SC.

  18. Low-cost flexible supercapacitors with high-energy density based on nanostructured MnO2 and Fe2O3 thin films directly fabricated onto stainless steel.

    PubMed

    Gund, Girish S; Dubal, Deepak P; Chodankar, Nilesh R; Cho, Jun Y; Gomez-Romero, Pedro; Park, Chan; Lokhande, Chandrakant D

    2015-01-01

    The facile and economical electrochemical and successive ionic layer adsorption and reaction (SILAR) methods have been employed in order to prepare manganese oxide (MnO2) and iron oxide (Fe2O3) thin films, respectively with the fine optimized nanostructures on highly flexible stainless steel sheet. The symmetric and asymmetric flexible-solid-state supercapacitors (FSS-SCs) of nanostructured (nanosheets for MnO2 and nanoparticles for Fe2O3) electrodes with Na2SO4/Carboxymethyl cellulose (CMC) gel as a separator and electrolyte were assembled. MnO2 as positive and negative electrodes were used to fabricate symmetric SC, while the asymmetric SC was assembled by employing MnO2 as positive and Fe2O3 as negative electrode. Furthermore, the electrochemical features of symmetric and asymmetric SCs are systematically investigated. The results verify that the fabricated symmetric and asymmetric FSS-SCs present excellent reversibility (within the voltage window of 0-1 V and 0-2 V, respectively) and good cycling stability (83 and 91%, respectively for 3000 of CV cycles). Additionally, the asymmetric SC shows maximum specific capacitance of 92 Fg(-1), about 2-fold of higher energy density (41.8 Wh kg(-1)) than symmetric SC and excellent mechanical flexibility. Furthermore, the "real-life" demonstration of fabricated SCs to the panel of SUK confirms that asymmetric SC has 2-fold higher energy density compare to symmetric SC. PMID:26208144

  19. Low-cost flexible supercapacitors with high-energy density based on nanostructured MnO2 and Fe2O3 thin films directly fabricated onto stainless steel

    PubMed Central

    Gund, Girish S.; Dubal, Deepak P.; Chodankar, Nilesh R.; Cho, Jun Y.; Gomez-Romero, Pedro; Park, Chan; Lokhande, Chandrakant D.

    2015-01-01

    The facile and economical electrochemical and successive ionic layer adsorption and reaction (SILAR) methods have been employed in order to prepare manganese oxide (MnO2) and iron oxide (Fe2O3) thin films, respectively with the fine optimized nanostructures on highly flexible stainless steel sheet. The symmetric and asymmetric flexible-solid-state supercapacitors (FSS-SCs) of nanostructured (nanosheets for MnO2 and nanoparticles for Fe2O3) electrodes with Na2SO4/Carboxymethyl cellulose (CMC) gel as a separator and electrolyte were assembled. MnO2 as positive and negative electrodes were used to fabricate symmetric SC, while the asymmetric SC was assembled by employing MnO2 as positive and Fe2O3 as negative electrode. Furthermore, the electrochemical features of symmetric and asymmetric SCs are systematically investigated. The results verify that the fabricated symmetric and asymmetric FSS-SCs present excellent reversibility (within the voltage window of 0–1 V and 0–2 V, respectively) and good cycling stability (83 and 91%, respectively for 3000 of CV cycles). Additionally, the asymmetric SC shows maximum specific capacitance of 92 Fg−1, about 2-fold of higher energy density (41.8 Wh kg−1) than symmetric SC and excellent mechanical flexibility. Furthermore, the “real-life” demonstration of fabricated SCs to the panel of SUK confirms that asymmetric SC has 2-fold higher energy density compare to symmetric SC. PMID:26208144

  20. REMOTELY RECHARGEABLE EPD

    SciTech Connect

    Vrettos, N; Athneal Marzolf, A; Scott Bowser, S

    2007-11-13

    Radiation measurements inside the Contact Decon Maintenance Cell (CDMC) in the Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS) are required to determine stay times for personnel. A system to remotely recharge the transmitter of an Electronic Personnel Dosimeter (EPD) and bail assembly to transport the EPD within the CDMC was developed by the Savannah River National Laboratory (SRNL) to address this need.

  1. Rechargeable Magnesium Power Cells

    NASA Technical Reports Server (NTRS)

    Koch, Victor R.; Nanjundiah, Chenniah; Orsini, Michael

    1995-01-01

    Rechargeable power cells based on magnesium anodes developed as safer alternatives to high-energy-density cells like those based on lithium and sodium anodes. At cost of some reduction in energy density, magnesium-based cells safer because less susceptible to catastrophic meltdown followed by flames and venting of toxic fumes. Other advantages include ease of handling, machining, and disposal, and relatively low cost.

  2. Recharge into a shingle beach

    NASA Astrophysics Data System (ADS)

    Keating, T.

    1984-04-01

    Traditionally, groundwater recharge in the U.K. has been calculated by the Penman method on a monthly basis, using values of potential evaporation derived from averaged meteorological data and monthly totals of rainfall. Recent work by K.W.F. Howard and J.W. Lloyd has shown that these monthly totals considerably underestimate recharge calculated over shorter time periods and they suggested that 1-day, or at worst, 10-day intervals should be used. In this paper field experiments to measure recharge into a shingle beach are reported. These experiments were made with a lysimeter over a 6-yr. period and have shown that recharge into the shingle occurs whenever significant precipitation occurs, even during the summer months. The Penman model is shown to be unrealistic for estimating recharge into such a beach and an alternative model for calculating recharge is proposed. This model is shown to yield good results.

  3. High psedocapacitance of MnO2 nanoparticles in graphitic disordered mesoporous carbon at high scan rates

    SciTech Connect

    Dai, Sheng; Patel, Mehul; Wang, Xiqing; Slanac, Daniel A; Ferrer, Domingo; Johnston, Keith; Stevenson, Keith J

    2012-01-01

    Nanocomposites composed of MnO{sub 2} and graphitic disordered mesoporous carbon (MnO{sub 2}/C) were synthesized for high total specific capacitance and redox pseudocapacitance (C{sub MnO{sub 2}}) at high scan rates up to 200 mV s{sup -1}. High resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray spectroscopy (EDX) demonstrated that MnO{sub 2} nanodomains were highly dispersed throughout the mesoporous carbon structure. According to HRTEM and X-ray diffraction (XRD), the MnO{sub 2} domains are shown to be primarily amorphous and less than 5 nm in size. For these composites in aqueous 1 M Na{sub 2}SO{sub 4} electrolyte, C{sub MnO{sub 2}} reached 500 F/g{sub MnO{sub 2}} at 2 mV s{sup -1} for 8.8 wt% MnO{sub 2}. A capacitance fade of only 20% over a 100-fold change in scan rate was observed for a high loading of 35 wt% MnO{sub 2} with a C{sub MnO{sub 2}} of 310 F/g{sub MnO{sub 2}} at the highest scan rate of 200 mV s{sup -1}. The high electronic conductivity of the graphitic 3D disordered mesoporous carbon support in conjunction with the thin MnO{sub 2} nanodomains facilitate rapid electron and ion transport offering the potential of improved high power density energy storage pseudocapacitors.

  4. High pseudocapacitance of MnO2 nanoparticles in graphitic disordered mesoporous carbon at high scan rates

    SciTech Connect

    Dai, Sheng; Patel, Mehul; Wang, Xiqing; Slanac, Daniel A; Ferrer, Domingo; Johnston, Keith

    2012-01-01

    Nanocomposites composed of MnO{sub 2} and graphitic disordered mesoporous carbon (MnO{sub 2}/C) were synthesized for high total specific capacitance and redox pseudocapacitance (C{sub MnO{sub 2}}) at high scan rates up to 200 mV s{sup -1}. High resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray spectroscopy (EDX) demonstrated that MnO{sub 2} nanodomains were highly dispersed throughout the mesoporous carbon structure. According to HRTEM and X-ray diffraction (XRD), the MnO{sub 2} domains are shown to be primarily amorphous and less than 5 nm in size. For these composites in aqueous 1 M Na{sub 2}SO{sub 4} electrolyte, C{sub MnO{sub 2}} reached 500 F/g{sub MnO{sub 2}} at 2 mV s{sup -1} for 8.8 wt% MnO{sub 2}. A capacitance fade of only 20% over a 100-fold change in scan rate was observed for a high loading of 35 wt% MnO{sub 2} with a C{sub MnO{sub 2}} of 310 F/g{sub MnO{sub 2}} at the highest scan rate of 200 mV s{sup -1}. The high electronic conductivity of the graphitic 3D disordered mesoporous carbon support in conjunction with the thin MnO{sub 2} nanodomains facilitate rapid electron and ion transport offering the potential of improved high power density energy storage pseudocapacitors.

  5. Recycling application of Li-MnO₂ batteries as rechargeable lithium-air batteries.

    PubMed

    Hu, Yuxiang; Zhang, Tianran; Cheng, Fangyi; Zhao, Qing; Han, Xiaopeng; Chen, Jun

    2015-03-27

    The ever-increasing consumption of a huge quantity of lithium batteries, for example, Li-MnO2 cells, raises critical concern about their recycling. We demonstrate herein that decayed Li-MnO2 cells can be further utilized as rechargeable lithium-air cells with admitted oxygen. We further investigated the effects of lithiated manganese dioxide on the electrocatalytic properties of oxygen-reduction and oxygen-evolution reactions (ORR/OER). The catalytic activity was found to be correlated with the composition of Li(x)MnO2 electrodes (0rechargeable lithium-air batteries. PMID:25678148

  6. Fluoride removal from water using activated and MnO2-coated Tamarind Fruit (Tamarindus indica) shell: batch and column studies.

    PubMed

    Sivasankar, V; Ramachandramoorthy, T; Chandramohan, A

    2010-05-15

    The present work is concerned with the defluoridation capacities of activated (ATFS) and MnO(2)-coated Tamarind Fruit Shell (MTFS), using batch and column sorption techniques. In the batch technique, the dynamics of fluoride sorption, with respect to pH, [F](o) and sorbent dose, was studied. The applicability of pseudo-first order for ATFS and Ritchie-second order for MTFS was observed. The kinetics data were found to fit well with Temkin isotherm for ATFS and Langmuir for MTFS. The interaction of co-ions in the defluoridation capacity of the sorbent was studied. Column experiments were carried out under a constant fluoride concentration of 2mg/l, flow rate and different bed depths. The capacities of the breakthrough and exhaustion points increased with increase in the bed depth for ATFS unlike MTFS. The Thomson model was applied to the column experimental results. The characterization of the sorbents, ATFS and MTFS, was done using the FTIR, SEM and XRD techniques. PMID:20071077

  7. A possible evolutionary origin for the Mn4 cluster of the photosynthetic water oxidation complex from natural MnO2 precipitates in the early ocean

    SciTech Connect

    Sauer, Kenneth; Yachandra, Vittal K.

    2002-04-30

    The photosynthetic water oxidation complex consists of a cluster of 4 Mn atoms bridged by O atoms, associated with Ca2+ and Cl- and incorporated into protein. The structure is similar in higher plants and algae, as well as in cyanobacteria of more ancient lineage, dating back more than 2.5 Ga on Earth. It has been proposed that the proto-enzyme derived from a component of a natural early marine manganese precipitate that contained a CaMn4O9 cluster. A variety of MnO2 minerals is found in nature. Three major classes are spinels, sheet-like layered structures and 3-dimensional networks that contain parallel tunnels. These relatively open structures readily incorporate cations (Na+, Li+, Mg2+, Ca2+, Ba2+, H+ and even Mn2+) and water. The minerals have different ratios of Mn(III) and Mn(IV) octahedrally coordinated to oxygens. Using X-ray spectroscopy we compare the chemical structures of Mn in the minerals with what is known about the arrangement in the water-oxidation complex to define the parameters of a structural model for the photosynthetic catalytic site. This comparison provides for the structural model a set of candidate Mn4 clusters -- some previously proposed and considered and others entirely novel.

  8. Molecular imprinting method for fabricating novel glucose sensor: polyvinyl acetate electrode reinforced by MnO2/CuO loaded on graphene oxide nanoparticles.

    PubMed

    Farid, Mohammad Masoudi; Goudini, Leila; Piri, Farideh; Zamani, Abbasali; Saadati, Fariba

    2016-03-01

    An enzyme free glucose sensor was prepared by a molecular imprinting method (MIP). The procedure was developed by in situ preparation of a new polyvinyl acetate (PVA) electrode reinforced by MnO2/CuO loaded on graphene oxide (GO) nanoparticles (PVA/MnO2@GO/CuO). The nanocomposite was modified in the presence of glucose and then imprinted. A carbone paste method with voltammetry was used in the fabrication of the sensor from prepared MIP nanocomposite. PVA/MnO2@GO/CuO electrode was characterized by X-ray diffraction, FT-IR spectroscopy and scanning electron microscopy. Electrocatalytic activity of the electrode toward glucose oxidation was then investigated by cyclic voltammetry in alkaline medium. The results show that the response of PVA/MnO2@GO/CuO MIP is much higher than PVA/MnO2@GO/CuO non-imprinted electrode toward glucose oxidation. The detection limit was 53μM, and the sensor responses are linear for concentrations from 0.5 to 4.4mM. Relative standard deviations for intra- and inter-day determination were less than 6.0%. The relative recoveries for different samples were 96%. PMID:26471527

  9. Evolution of strategies for modern rechargeable batteries.

    PubMed

    Goodenough, John B

    2013-05-21

    This Account provides perspective on the evolution of the rechargeable battery and summarizes innovations in the development of these devices. Initially, I describe the components of a conventional rechargeable battery along with the engineering parameters that define the figures of merit for a single cell. In 1967, researchers discovered fast Na(+) conduction at 300 K in Na β,β''-alumina. Since then battery technology has evolved from a strongly acidic or alkaline aqueous electrolyte with protons as the working ion to an organic liquid-carbonate electrolyte with Li(+) as the working ion in a Li-ion battery. The invention of the sodium-sulfur and Zebra batteries stimulated consideration of framework structures as crystalline hosts for mobile guest alkali ions, and the jump in oil prices in the early 1970s prompted researchers to consider alternative room-temperature batteries with aprotic liquid electrolytes. With the existence of Li primary cells and ongoing research on the chemistry of reversible Li intercalation into layered chalcogenides, industry invested in the production of a Li/TiS2 rechargeable cell. However, on repeated recharge, dendrites grew across the electrolyte from the anode to the cathode, leading to dangerous short-circuits in the cell in the presence of the flammable organic liquid electrolyte. Because lowering the voltage of the anode would prevent cells with layered-chalcogenide cathodes from competing with cells that had an aqueous electrolyte, researchers quickly abandoned this effort. However, once it was realized that an oxide cathode could offer a larger voltage versus lithium, researchers considered the extraction of Li from the layered LiMO2 oxides with M = Co or Ni. These oxide cathodes were fabricated in a discharged state, and battery manufacturers could not conceive of assembling a cell with a discharged cathode. Meanwhile, exploration of Li intercalation into graphite showed that reversible Li insertion into carbon occurred

  10. FLUIDIC: Metal Air Recharged

    SciTech Connect

    Friesen, Cody

    2014-03-07

    Fluidic, with the help of ARPA-E funding, has developed and deployed the world's first proven high cycle life metal air battery. Metal air technology, often used in smaller scale devices like hearing aids, has the lowest cost per electron of any rechargeable battery storage in existence. Deploying these batteries for grid reliability is competitive with pumped hydro installations while having the advantages of a small footprint. Fluidic's battery technology allows utilities and other end users to store intermittent energy generated from solar and wind, as well as maintain reliable electrical delivery during power outages. The batteries are manufactured in the US and currently deployed to customers in emerging markets for cell tower reliability. As they continue to add customers, they've gained experience and real world data that will soon be leveraged for US grid reliability.

  11. FLUIDIC: Metal Air Recharged

    ScienceCinema

    Friesen, Cody

    2014-04-02

    Fluidic, with the help of ARPA-E funding, has developed and deployed the world's first proven high cycle life metal air battery. Metal air technology, often used in smaller scale devices like hearing aids, has the lowest cost per electron of any rechargeable battery storage in existence. Deploying these batteries for grid reliability is competitive with pumped hydro installations while having the advantages of a small footprint. Fluidic's battery technology allows utilities and other end users to store intermittent energy generated from solar and wind, as well as maintain reliable electrical delivery during power outages. The batteries are manufactured in the US and currently deployed to customers in emerging markets for cell tower reliability. As they continue to add customers, they've gained experience and real world data that will soon be leveraged for US grid reliability.

  12. Preparation of polyacrylnitrile (PAN)/ Manganese oxide based activated carbon nanofibers (ACNFs) for adsorption of Cadmium (II) from aqueous solution

    NASA Astrophysics Data System (ADS)

    Abdullah, N.; Yusof, N.; Jaafar, J.; Ismail, AF; Che Othman, F. E.; Hasbullah, H.; Salleh, W. N. W.; Misdan, N.

    2016-06-01

    In this work, activated carbon nanofibers (ACNFs) from precursor polyacrylnitrile (PAN) and manganese oxide (MnO2) were prepared via electrospinning process. The electrospun PAN/MnO2-based ACNFs were characterised in term of its morphological structure and specific surface area using SEM and BET analysis respectively. The comparative adsorption study of cadmium (II) ions from aqueous solution between the neat ACNFs, composite ACNFs and commercial granular activated carbon was also conducted. SEM analysis illustrated that composite ACNFs have more compact fibers with presence of MnO2 beads with smaller fiber diameter of 437.2 nm as compared to the neat ACNFs which is 575.5 nm. BET analysis elucidated specific surface area of ACNFs/MnO2 to be 67 m2/g. Under adsorption study, it was found out that Cd (II) removal by ACNFs/MnO2 was the highest (97%) followed by neat ACNFs (96%) and GAC (74%).

  13. Prototype systems for rechargeable magnesium batteries.

    PubMed

    Aurbach, D; Lu, Z; Schechter, A; Gofer, Y; Gizbar, H; Turgeman, R; Cohen, Y; Moshkovich, M; Levi, E

    2000-10-12

    The thermodynamic properties of magnesium make it a natural choice for use as an anode material in rechargeable batteries, because it may provide a considerably higher energy density than the commonly used lead-acid and nickel-cadmium systems. Moreover, in contrast to lead and cadmium, magnesium is inexpensive, environmentally friendly and safe to handle. But the development of Mg batteries has been hindered by two problems. First, owing to the chemical activity of Mg, only solutions that neither donate nor accept protons are suitable as electrolytes; but most of these solutions allow the growth of passivating surface films, which inhibit any electrochemical reaction. Second, the choice of cathode materials has been limited by the difficulty of intercalating Mg ions in many hosts. Following previous studies of the electrochemistry of Mg electrodes in various non-aqueous solutions, and of a variety of intercalation electrodes, we have now developed rechargeable Mg battery systems that show promise for applications. The systems comprise electrolyte solutions based on Mg organohaloaluminate salts, and Mg(x)Mo3S4 cathodes, into which Mg ions can be intercalated reversibly, and with relatively fast kinetics. We expect that further improvements in the energy density will make these batteries a viable alternative to existing systems. PMID:11048714

  14. Amperometric determination of bonded glucose with an MnO(2) and glucose oxidase bulk-modified screen-printed electrode using flow-injection analysis.

    PubMed

    Turkusic, Emir; Kalcher, Josef; Kahrovic, Emira; Beyene, Negussie W; Moderegger, Helmut; Sofic, Emin; Begic, Sabina; Kalcher, Kurt

    2005-01-30

    A screen-printed amperometric biosensor based on carbon ink double bulk-modified with MnO(2) as a mediator and glucose oxidase as a biocomponent was investigated for its ability to serve as a detector for bonded glucose in different compounds, such as cellobiose, saccharose, (-)-4-nitrophenyl-beta-d-glucopyranoside, as well as in beer samples by flow-injection analysis (FIA). The biosensor could be operated under physiological conditions (0.1M phosphate buffer, pH 7.5) and exhibited good reproducibility and stability. Bonded glucose was released with glucosidase in solution, and the free glucose was detected with the modified screen-printed electrode (SPE). The release of glucose by the aid of glucosidase from cellobiose, saccharose and (-)-4-nitrophenyl-beta-d-glucopyranoside in solution showed that stoichiometric quantities of free glucose could be monitored in all three cases. The linear range of the amperometric response of the biosensor in the FIA-mode flow rate 0.2mLmin(-1), injection volume 0.25mL, operation potential 0.48V versus Ag/AgCl) extends from 11 to 13,900mumolL(-1) glucose in free form. The limit of detection (3sigma) is 1mumolL(-1) glucose. A concentration of 100mumolL(-1) yields a relative standard deviation of approximately 7% with five injections. These values correspond to the same concentrations of bonded glucose supposed that it is liberated quantitatively (incubation for 2h with glucosidase). Bonded glucose could be determined in beer samples using the same assay. The results corresponded very well with the reference procedure. PMID:18969835

  15. Thermally-Rechargeable Electrochemical Cell

    NASA Technical Reports Server (NTRS)

    Richter, R.

    1985-01-01

    Proposed liquid-sodium/sulfur electrochemical cell recharged by heat, rather than electric generator. Concept suitable for energy storage for utilites, mobile electronic equipment, and solar thermoelectric power systems. Sodium ions driven across membrane with aid of temperature differential.

  16. Chemically rechargeable battery

    NASA Technical Reports Server (NTRS)

    Graf, James E. (Inventor); Rowlette, John J. (Inventor)

    1984-01-01

    Batteries (50) containing oxidized, discharged metal electrodes such as an iron-air battery are charged by removing and storing electrolyte in a reservoir (98), pumping fluid reductant such as formalin (aqueous formaldehyde) from a storage tank (106) into the battery in contact with the surfaces of the electrodes. After sufficient iron hydroxide has been reduced to iron, the spent reductant is drained, the electrodes rinsed with water from rinse tank (102) and then the electrolyte in the reservoir (106) is returned to the battery. The battery can be slowly electrically charged when in overnight storage but can be quickly charged in about 10 minutes by the chemical procedure of the invention.

  17. Functional materials for rechargeable batteries.

    PubMed

    Cheng, Fangyi; Liang, Jing; Tao, Zhanliang; Chen, Jun

    2011-04-19

    There is an ever-growing demand for rechargeable batteries with reversible and efficient electrochemical energy storage and conversion. Rechargeable batteries cover applications in many fields, which include portable electronic consumer devices, electric vehicles, and large-scale electricity storage in smart or intelligent grids. The performance of rechargeable batteries depends essentially on the thermodynamics and kinetics of the electrochemical reactions involved in the components (i.e., the anode, cathode, electrolyte, and separator) of the cells. During the past decade, extensive efforts have been dedicated to developing advanced batteries with large capacity, high energy and power density, high safety, long cycle life, fast response, and low cost. Here, recent progress in functional materials applied in the currently prevailing rechargeable lithium-ion, nickel-metal hydride, lead acid, vanadium redox flow, and sodium-sulfur batteries is reviewed. The focus is on research activities toward the ionic, atomic, or molecular diffusion and transport; electron transfer; surface/interface structure optimization; the regulation of the electrochemical reactions; and the key materials and devices for rechargeable batteries. PMID:21394791

  18. Mechanism of sonochemical reduction of permanganate to manganese dioxide in aqueous alcohol solutions: Reactivities of reducing species formed by alcohol sonolysis.

    PubMed

    Okitsu, Kenji; Iwatani, Masaki; Okano, Koji; Uddin, Md Helal; Nishimura, Rokuro

    2016-07-01

    The sonochemical reduction of MnO4(-) to MnO2 in aqueous solutions was investigated as a function of alcohol concentration under Ar. The rate of MnO4(-) reduction initially decreased with increasing alcohol concentration, and then increased when the alcohol concentration was increased further. The concentrations at which the reduction rates were minimum depended on the hydrophobic properties of the added alcohols under ultrasonic irradiation. At low concentrations, the alcohols acted as OH radical scavengers; at high concentrations, they acted as reductant precursors: Rab, formed by abstraction reactions of the alcohols with sonochemically formed OH radicals or H atoms, and Rpy, formed by alcohol pyrolysis under ultrasonic irradiation. The results suggest that the reactivity order of the sonochemically formed reducing species with MnO4(-) at pH 7-9 is the sum of H2O2 and H>Rpy>Rab. The peak wavelengths of MnO2 colloidal solutions formed at high 1-butanol concentrations shifted to shorter wavelengths, suggesting the formation of small particles at high 1-butanol concentrations. The rates of sonochemical reduction of MnO2 to Mn(2+) in the presence of 1-butanol were slower than that in the absence of 1-butanol, because the sonochemical formation of H2O2 and H, which act as reductants, was suppressed by 1-butanol in aqueous solutions. PMID:26964972

  19. Hybrid system for rechargeable magnesium battery with high energy density.

    PubMed

    Chang, Zheng; Yang, Yaqiong; Wang, Xiaowei; Li, Minxia; Fu, Zhengwen; Wu, Yuping; Holze, Rudolf

    2015-01-01

    One of the main challenges of electrical energy storage (EES) is the development of environmentally friendly battery systems with high safety and high energy density. Rechargeable Mg batteries have been long considered as one highly promising system due to the use of low cost and dendrite-free magnesium metal. The bottleneck for traditional Mg batteries is to achieve high energy density since their output voltage is below 2.0 V. Here, we report a magnesium battery using Mg in Grignard reagent-based electrolyte as the negative electrode, a lithium intercalation compound in aqueous solution as the positive electrode, and a solid electrolyte as a separator. Its average discharge voltage is 2.1 V with stable discharge platform and good cycling life. The calculated energy density based on the two electrodes is high. These findings open another door to rechargeable magnesium batteries. PMID:26173624

  20. Novel electrolyte chemistries for Mg-Ni rechargeable batteries.

    SciTech Connect

    Garcia-Diaz, Brenda; Kane, Marie; Au, Ming

    2010-10-01

    Commercial hybrid electric vehicles (HEV) and battery electric vehicles (BEV) serve as means to reduce the nation's dependence on oil. Current electric vehicles use relatively heavy nickel metal hydride (Ni-MH) rechargeable batteries. Li-ion rechargeable batteries have been developed extensively as the replacement; however, the high cost and safety concerns are still issues to be resolved before large-scale production. In this study, we propose a new highly conductive solid polymer electrolyte for Mg-Ni high electrochemical capacity batteries. The traditional corrosive alkaline aqueous electrolyte (KOH) is replaced with a dry polymer with conductivity on the order of 10{sup -2} S/cm, as measured by impedance spectroscopy. Several potential novel polymer and polymer composite candidates are presented with the best-performing electrolyte results for full cell testing and cycling.

  1. Hybrid system for rechargeable magnesium battery with high energy density

    PubMed Central

    Chang, Zheng; Yang, Yaqiong; Wang, Xiaowei; Li, Minxia; Fu, Zhengwen; Wu, Yuping; Holze, Rudolf

    2015-01-01

    One of the main challenges of electrical energy storage (EES) is the development of environmentally friendly battery systems with high safety and high energy density. Rechargeable Mg batteries have been long considered as one highly promising system due to the use of low cost and dendrite-free magnesium metal. The bottleneck for traditional Mg batteries is to achieve high energy density since their output voltage is below 2.0 V. Here, we report a magnesium battery using Mg in Grignard reagent-based electrolyte as the negative electrode, a lithium intercalation compound in aqueous solution as the positive electrode, and a solid electrolyte as a separator. Its average discharge voltage is 2.1 V with stable discharge platform and good cycling life. The calculated energy density based on the two electrodes is high. These findings open another door to rechargeable magnesium batteries. PMID:26173624

  2. Fabrication of Polypyrrole/Graphene Oxide Composite Nanosheets and Their Applications for Cr(VI) Removal in Aqueous Solution

    PubMed Central

    Li, Shangkun; Lu, Xiaofeng; Xue, Yanpeng; Lei, Junyu; Zheng, Tian; Wang, Ce

    2012-01-01

    In this paper, we report on the simple, reliable synthesis of polypyrrole (PPy)/graphene oxide (GO) composite nanosheets by using sacrificial-template polymerization method. Herein, MnO2 nanoslices were chosen as a sacrificial-template to deposit PPy, which served as the oxidant as well. During the polymerization of pyrrole on surface of GO nanosheets, MnO2 component was consumed incessantly. As a result, the PPy growing on the surface of GO nanosheets has the morphology just like the MnO2 nanoslices. This method can provide the fabrication of PPy nanostructures more easily than conventional route due to its independence of removing template, which usually is a complex and tedious experimental process. The as-prepared PPy/GO composite nanosheets exhibited an enhanced properties for Cr(VI) ions removal in aqueous solution based on the synergy effect. The adsorption capacity of the PPy/GO composite nanosheets is about two times as large as that of conventional PPy nanoparticles. We believe that our findings can open a new and effective avenue to improve the adsorption performance in removing heavy metal ions from waste water. PMID:22927957

  3. Choosing appropriate techniques for quantifying groundwater recharge

    USGS Publications Warehouse

    Scanlon, B.R.; Healy, R.W.; Cook, P.G.

    2002-01-01

    Various techniques are available to quantify recharge; however, choosing appropriate techniques is often difficult. Important considerations in choosing a technique include space/time scales, range, and reliability of recharge estimates based on different techniques; other factors may limit the application of particular techniques. The goal of the recharge study is important because it may dictate the required space/time scales of the recharge estimates. Typical study goals include water-resource evaluation, which requires information on recharge over large spatial scales and on decadal time scales; and evaluation of aquifer vulnerability to contamination, which requires detailed information on spatial variability and preferential flow. The range of recharge rates that can be estimated using different approaches should be matched to expected recharge rates at a site. The reliability of recharge estimates using different techniques is variable. Techniques based on surface-water and unsaturated-zone data provide estimates of potential recharge, whereas those based on groundwater data generally provide estimates of actual recharge. Uncertainties in each approach to estimating recharge underscore the need for application of multiple techniques to increase reliability of recharge estimates.

  4. Reusable Energy and Power Sources: Rechargeable Batteries

    ERIC Educational Resources Information Center

    Hsiung, Steve C.; Ritz, John M.

    2007-01-01

    Rechargeable batteries are very popular within consumer electronics. If one uses a cell phone or portable electric tool, she/he understands the need to have a reliable product and the need to remember to use the recharging systems that follow a cycle of charge/discharge. Rechargeable batteries are being called "green" energy sources. They are a…

  5. Rechargeable nickel-zinc batteries

    NASA Technical Reports Server (NTRS)

    Soltis, D. G.

    1977-01-01

    Device proves superiority in having two and one half to three times the energy content of popular lead-zinc or nickel-cadmium batteries. Application to electric utility vehicles improved acceleration rate and nearly doubled driving range between rechargings. Unit contributes substantially toward realization of practical urban electrical automobiles.

  6. Hierarchically MnO2-Nanosheet Covered Submicrometer-FeCo2O4-Tube Forest as Binder-Free Electrodes for High Energy Density All-Solid-State Supercapacitors.

    PubMed

    Zhu, Baogang; Tang, Shaochun; Vongehr, Sascha; Xie, Hao; Meng, Xiangkang

    2016-02-01

    The current problem of the still relatively low energy densities of supercapacitors can be effectively addressed by designing electrodes hierarchically on micro- and nanoscale. Herein, we report the synthesis of hierarchically porous, nanosheet covered submicrometer tube forests on Ni foam. Chemical deposition and thermal treatment result in homogeneous forests of 750 nm diameter FeCo2O4 tubes, which after hydrothermal reaction in KMnO4 are wrapped in MnO2-nanosheet-built porous covers. The covers' thickness can be adjusted from 200 to 800 nm by KMnO4 concentration. An optimal thickness (380 nm) with a MnO2 content of 42 wt % doubles the specific capacitance (3.30 F cm(-2) at 1.0 mA cm(-2)) of the bare FeCo2O4-tube forests. A symmetric solid-state supercapacitor made from these binder-free electrodes achieves 2.52 F cm(-2) at 2 mA cm(-2), much higher than reported for capacitors based on similar core-shell nanowire arrays. The large capacitance and high cell voltage of 1.7 V allow high energy and power densities (93.6 Wh kg(-1), 10.1 kW kg(-1)). The device also exhibits superior rate capability (71% capacitance at 20 mA cm(-2)) and remarkable cycling stability with 94% capacitance retention being stable after 1500 cycles. PMID:26824784

  7. Non-aqueous electrolyte for high voltage rechargeable magnesium batteries

    DOEpatents

    Doe, Robert Ellis; Lane, George Hamilton; Jilek, Robert E; Hwang, Jaehee

    2015-02-10

    An electrolyte for use in electrochemical cells is provided. The properties of the electrolyte include high conductivity, high Coulombic efficiency, and an electrochemical window that can exceed 3.5 V vs. Mg/Mg.sup.+2. The use of the electrolyte promotes the electrochemical deposition and dissolution of Mg without the use of any Grignard reagents, other organometallic materials, tetraphenyl borate, or tetrachloroaluminate derived anions. Other Mg-containing electrolyte systems that are expected to be suitable for use in secondary batteries are also described.

  8. Identifying Groundwater Recharge in Arid Regions

    NASA Astrophysics Data System (ADS)

    Thomas, B. F.; Famiglietti, J. S.

    2015-12-01

    Recharge epodicity in arid regions provides a method to estimate annual groundwater recharge given a relationship expressed as the recharge to precipitation ratio. Traditionally, in-situ observations are required to identify aquifer recharge events, while more advanced approaches such as the water-table fluctuation method or the episodic master recession method are necessary to delineate the recharge event. Our study uses the Gravity Recovery and Climate Experiment (GRACE) observations to estimate monthly changes in groundwater storage which are attributed to the combination of groundwater abstraction and episodic recharge in the arid southwestern United States. Our results illustrate the ability of remote sensing technologies to identify episodic groundwater recharge in arid regions which can be used within sustainable groundwater management frameworks to effectively manage groundwater resources.

  9. Electrically rechargeable REDOX flow cell

    NASA Technical Reports Server (NTRS)

    Thaller, L. H. (Inventor)

    1976-01-01

    A bulk energy storage system is designed with an electrically rechargeable reduction-oxidation (REDOX) cell divided into two compartments by a membrane, each compartment containing an electrode. An anode fluid is directed through the first compartment at the same time that a cathode fluid is directed through the second compartment. Means are provided for circulating the anode and cathode fluids, and the electrodes are connected to an intermittent or non-continuous electrical source, which when operating, supplies current to a load as well as to the cell to recharge it. Ancillary circuitry is provided for disconnecting the intermittent source from the cell at prescribed times and for circulating the anode and cathode fluids according to desired parameters and conditions.

  10. Nanomaterials for rechargeable lithium batteries.

    PubMed

    Bruce, Peter G; Scrosati, Bruno; Tarascon, Jean-Marie

    2008-01-01

    Energy storage is more important today than at any time in human history. Future generations of rechargeable lithium batteries are required to power portable electronic devices (cellphones, laptop computers etc.), store electricity from renewable sources, and as a vital component in new hybrid electric vehicles. To achieve the increase in energy and power density essential to meet the future challenges of energy storage, new materials chemistry, and especially new nanomaterials chemistry, is essential. We must find ways of synthesizing new nanomaterials with new properties or combinations of properties, for use as electrodes and electrolytes in lithium batteries. Herein we review some of the recent scientific advances in nanomaterials, and especially in nanostructured materials, for rechargeable lithium-ion batteries. PMID:18338357