Graphene for supercapacitor application Maria Sarno

Size: px

Start display at page:

Download "Graphene for supercapacitor application Maria Sarno"

Hector Edwards
5 years ago
Views:

1 University of Salerno Graphene for supercapacitor application Maria Sarno Prof. Maria Sarno Professor of Chemical Engineering Director of NANO_MATES (Research Centre for NANOMAterials and nanotechnology at Salerno Univerity).

2 «Measurement of the quantum capacitance of graphene» Xia J. et al., Nat Nanotechnol, 29. «Graphene-Based Supercapacitor with an Ultrahigh Energy Density» LiuC.etal.,J.NANOLETT,21. «Ultrathin Planar Graphene Supercapacitor» YooJ.etal.,NANOLETT,211. «Electrochemical properties for high surface area and improved electrical conductivity of platium-embedded porous carbon nanofibers» AnG.-H.etal.,JPOWERSOURCES,212.

3 University of Salerno Core shell graphene coated FeCo nanoparticles (GFeCo) M. Sarno et al., Electrochemical Applications of Magnetic Core Shell Graphene-Coated FeCo Nanoparticles, Ind. Eng. Chem. Res., 216, 55(11), pp

4 Graphene & Metal/Graphene composites for supercapacitors: STATE OF ART Electrochemical Applications of Magnetic Core Shell Graphene-Coated FeCo Nanoparticles, Maria Sarno et al., Ind. Eng. Chem. Res.,216.. «Novel Cd-doped Co/C nanoparticles for Electrochemical Supercapacitors» Barakat et al., MATER LETT, 213. «Silver nanoparticles decorated on a three-dimensional graphene scaffold for electrochemical applications» BelloA.etal.,JPHYS.CHEM.SOLIDS,214. «Nitrogen-doped, FeNi alloy nanoparticle-decorated graphene as an efficient and electrode for electrochemical supercapacitors in acid medium» El-Deen et al., NANOSCALE RES LETT, 215.

5 Nanoparticles Results & Discussion SYNTHESIS AND CHARACTERIZATION Core shell graphene coated FeCo nanoparticles have been prepared by a catalytic chemical vapor deposition(ccvd) of methane on a FeCo catalyst in the channels of an alumina support. TEM images X Ray Diffraction Pattern 5 nm Intensity (a.u.) (11) f (2) (211) 1-2 graphene layers GCMNPN θ 2Q Raman Spectrum Counts Diameter [nm] Intensity (a.u.) G D Raman Shift cm -1 Wavenumber (cm-1) 2D

6 C= 367,2 F/g at,9 A/g Galvanostatic Charge/Discharge Tests

7 University of Salerno Graphene based Electrode Materials M. Sarno et al., Supercritical CO 2 processing to improve the electrochemical properties of graphene oxide, J. of Supercritical Fluids 216, 118,

8 SC-CO2 PROCESS FOR GRAPHENE-based SUPERCAPACITORS ELECTRODEs: STATE OF ART About SC-CO2 PROCESS FOR GRAPHENE-based SUPERCAPACITORS ELECTRODEs: «Preparation of graphene oxide/polyaniline nanocomposite with assistance of supercritical carbon dioxide for supercapacitor electrodes» G. Xu et al., Ind. Eng. Chem. Res. 212 «Supercritical CO 2 processingtoimprovetheelectrochemical properties ofgrapheneoxide» M.Sarnoetal.,J.ofSupercritical Fluids216 Characterization Mesoporous reduced graphene structures at different oxidation levels,have been obtained by SC-CO 2 assisted processdifferent durations up to 24 h. It is investigated the effect of SC-CO 2 processing on GO to produce a mesoporous reduced and exfoliated graphene structure with high surface area and excellent electrochemical performance. GO GO f rgo-sc 24h

9 C=O COOH OH of carboxyl group C=C C=C C-O-C C-O-C Typical contributions from hydroxyl (C-OH), ketonic species (C-O), carboxyl (COOH), sp 2 -hybridized C=C (in-plane vibrations), epoxide (C-O-C) and various C=O and C-O containing chemical species such as lactol, peroxide, dioxolane, anhydride and cyclic ether

10 Current (A/g) Electrochemical characterization 1/2 CYCLIC VOLTAMMETRY (a) GALVANOSTATIC CURVES (b, c) GO GO-SC3h GO-SC24h Voltage / V 1,,8,6,4 4 A/g 1,7 A/g,5 A/g rgo-sc 3h -2-3,,2,4,6,8 1, Potential (V) At the same current density (1.7 A/g) the specific capacitance of rgo-sc 24h (253 F/g) results about three times larger than the one exhibited by rgo- SC3h(86F/g). a Voltage / V,2, ,,8,6,4,2 Time / s 4,5 A/g 1,7 A/g 1 A/g, Time / s b rgo-sc 24h c

11 Electrochemical characterization 2/2 Specific Capacitance / Fg GO-SC 24 h GO-SC 3h Capacitance retention / % GO-SC 24h GO-SC 3h , Current density / Ag -1 5,x1 2 1,x1 3 1,5x1 3 2,x1 3 2,5x1 3 Cycles

12 Graphenebasedmaterialsto realize: a Novel Compact Supercapacitors M. Sarno et al., SC-CO2-assisted process for a high energy density aerogel supercapacitor: The effect of GO loading, Nanotechnology 217, 28(2).

13 Compact Supercapcitor Devices: STATE OF ART Electrodes with PVDF-HFP Poly(vinylidene fluoride-co-hexafluoropropylene) as electrode binder: Supercapacitors from Activated Carbon Derived from Banana Fibers Subramanian V,etal.,J.Phys.Chem.C, 27. Supercapacitors Devices with PVDF-HFP in gel polymer electrolyte: Electrochemical redox supercapacitors using PVdF-HFP based gel electrolytes and polypyrrole as conducting polymer electrode Tripathi et al, Solid State Ionics, 26. Studies on redox supercapacitor using electrochemically synthesized polypyrrole as electrode material using blend polymer gel electrolyte Tripathi et al., Indian J. Pure Appl. Phys, 213. High-performanceflexiblesolid-statesupercapacitorsbasedonMnO 2 -decoratednanocarbonelectrodes GaoY,etal.,RSCAdv.213 Ionic Liquid Directed Mesoporous Carbon Nanoflakes as an Effiencient Electrode material KongLandChenWSci.Rep.215 Others Supercapacitors Devices: «All-solid-state asymmetric supercapacitor based on reduced graphene oxide/carbon nanotube and carbon fiber paper/polypyrrole electrodes Yang C, et al., J. Mater. Chem. A, 214»

14 New Compact Supercapacitor Device Acetone GO b Sonication < c Sonicated nanoparticles Acetone PVDF-HFP Ethanol a SEM images PVDF_HFP PVDF_HFP_GO3 Materials: GO prepared with Hummers method modified Poly-vinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) immersed in 1- ethyl-3-methylimidazoliumtetrafluoroborate,(emimbf 4 ). PVDF-HFP_GOnanocompositeaerogel immersedin(emimbf 4 ). b d Porosity (%) Porous volume c < PVDF_HFP_GO6 PVDF_HFP_GO9 Electrolyte uptake (%) GO amount in aerogel (w/w) Electrolyte Uptake (E u) PVDF-HFP PVDF-HFP_GO1 PVDF-HFP_GO3 PVDF-HFP_GO6 PVDF-HFP_GO9 E u = (W w W d )/ W d 1% Time (min) Time (min)

15 Electrochemical Characterizations Current (A/g) 3x1 1 2x1 1 1x1 1-1x1 1-2x1 1-3x1 1 a 5 mv/sec PVDF-HFP_GO1_SC PVDF-HFP_GO6_SC PVDF-HFP_GO9_SC Potential (V) CV Curves Current (A/g) 5x1 1 4x1 1 3x1 1 2x1 1 1x1 1-1x1 1-2x1 1-3x1 1-4x1 1-5x1 1 b PVDF-HFP_GO6_SC 1 mv/sec 2 mv/sec 5 mv/sec 1 mv/sec 15 mv/sec Potential (V) Potential (V) 2 GDC Tests c 6 A/g 4 A/g 2 A/g 1 A/g,5 A/g Time (sec) Specific Capacitance Vs Current density Capacitance (F/g) d Current density (A/g) C= 83 F/g E=79.2 Wh/kg P= 234 W/Kg at the current density of.5 A/g Power density (W/kg) e Ragone Plot Energy density (Wh/kg) Current density (A/g) Energy density (Wh/kg) Capacitance retention / % Capacitance retentetion Potential (V) Time (sec), 5,x1 4 1,x1 5 Cycles Z'' (ohm) Z'' (ohm) Z' (ohm) PVDF-HFP_GO6 PVDF-HFP_GO6 after 5*1 4 cycles Cyclic voltammogram (CV) of PVDF-HFP_GO1, PVDF-HFP_GO6 and PVDF-HFP_GO9 at 5 mv/s between-2 V and 2V (a). CV of PVDF-HFP_GO6 at different scan rate between -2 V and 2V (b). Galvanostatic charge-discharge (GCD) curves of PVDF-HFP_GO6 at different current density between -2 V and 2V (c). Specific capacitance at different current density (d). Ragone plot. Insert showing energy density as a function of current density (e). Cycling life test of PVDF- HFP_GO6 at 6A/g(f). Nyquist plot before and after GCD cycling(g). f g Z' (ohm)

16 In summary Controlled size, structure, and morphology core shell 1 2 layer graphene-coated metallic nanoparticles have been prepared by methane CCVD at atmospheric pressure. Electrochemical tests show ideal capacity behavior, efficient energy storage, and excellent cycling stability. Such high supercapacitor performance can be attributed to the high electric double-layer contribution ensured by the micro-mesoporosity, with a high effective surface area and excellent electrical transport of the conductive network. Feasibility of a SC-CO 2 assisted process to reduce and exfoliate GO powders, obtaining porous and three-dimensional architectures formed by curved graphene sheets. Supercapacitors have been assembles in a sandwich design formed by three porous layers.

17 Other Materials

18 ELECTRODES MoS 2 MoS 2 /FLG MoS 2 /MoO 2 /FLG Carbon nanotubes Flexible Supercapacitors with others nanomaterials, such as : Fe 3 O 4 MoS 2 NiMoS Ag/graphene RuO 2 /Os MoS 2 /Fe 3 O 4.

19 Acknowledgement Eng. Carmela Scudieri Eng. Marcello Casa Eng. Claudia Cirillo Eng. Mariagrazia Iuliano Eng. Waleed Abdalglil Mustafa Eng. Eleonora Ponticorvo Eng. Davide Scarpa Eng. Domenico Spina Eng. Alfonso Troisi Eng. Gianluca Viscusi Prof. Paolo Ciambelli Prof. Ernesto Reverchon and his research group Thank you for your attention

Materials and Structural Design for Advanced Energy Storage Devices

Materials and Structural Design for Advanced Energy Storage Devices Imran Shakir Sustainable Energy Technologies Center (SET) King Saud University Saudi Arabia Specific Power (W/kg) Introduction and Motivation