Rational design of nanostructured electrode materials for highperformance supercapacitors by xingye fan a thesis presented to the university of waterloo in fulfillment of the thesis requirement for the degree of master of applied science in chemical engineering waterloo, ontario, canada, 2015 xingye fan 2015. Understanding the pseudocapacitance of ruo 2 from joint density functional theory cheng zhan and deen jiang department of chemistry, university of california, riverside, 92521, ca, usa. Electrochemical measurements the electrochemical properties of the asobtained carbon materials were tested using them as a single electrode in a threeelectrode system. The fundamentals of density functional theory revised and. Activated graphenebased carbons as supercapacitor electrodes. Understanding the pseudocapacitance of ruo from joint. Pdf a first principle study of graphenemetaloxides as nano. Properties and applications of supercapacitors from the state.
Nitrogendoped activated carbon for high energy hybridtype supercapacitor. The energy density in a battery may rise to 150 whkg. Pore size distributions were calculated by using the density functional theory dft. A density functional approach on the hexagonal graphene lattice is developed using an exact numerical solution to the hubbard model as the reference system. However, a thorough understanding of its atomicscale surface properties is lacking, which we address here using density functional theory dft. G h on the adsorption sites of heteroatomdoped structures are shown in fig. Dft calculations are hard to be extended to a realistic representation of the porous electrodes or complex ion structures owing to the huge computational costs. Chemical and electrochemical ageing of carbon materials used.
Most commercially available supercapacitors contain expensive electrolytes and costly electrode materials. For more intensive coverages of the subject, see e. Based on a coarsegrained model using classical density functional theory, we study the structure, ion partitioning, and selectivity of symmetric and asymmetric ionic liquid mixtures for both zero and nonzero applied potential. To design materials and interfaces for supercapacitor with higher energy density requires a deeper understanding of the factors and contributions affecting the total capacitance. So supercapacitor holds properties of both conventional. Supercapacitors theoretical and practical solutions. Density functional theory dft simulations revealed that bulk structures of both co 3 s 4 and co 3 o 4 have an antiferromagnetic afm configuration with co atoms at the tetrahedral site having an opposite spin. This paper provides the theoretical basis of density functional theory, which is now the most used method for characterizing the surface area of microporous carbons. Understanding the pseudocapacitance of ruo from joint density. Density functional theory calculations of the quantum capacitance of graphene oxide as a supercapacitor electrode ce song school of mathematical sciences, dalian university of technology, no. They are recommended for automobiles, tramways, buses, cranes, forklifts, wind turbines. Supercapacitors scs are very promising energy storage devices in different areas such as defense, communication, transportation, consumer electronics, and electricity applications owing to their long cycle life, good safety, simple mechanism, short charging time, and high power density. To this end, density functional theory dft could be a realistic tool for early prediction of the properties of supercapacitor electrode materials. This presentation does not contain any proprietary or confidential information.
G h for all the sites of the possible xg structures under an applied potential of u a 0. The most common electrical energy storage device used in vehicles is a battery. Exploring electrolyte organization in supercapacitor. Energy density describes how much energy can be stored per unit volume. Pore size distribution analysis of microporous carbons. Supercapacitor construction what makes supercapacitors different from other capacitors types are the electrodes used in these capacitors. The fabricated supercapacitor displayed an energy density of 26. Kumta i n the ongoing effort for energy sustainability, electrochemical supercapacitors are emerging as devices of prime importance owing to their superior characteristics unmatched. Although classical simulations and theory have been successfully applied to model edlcs,3141 a first principles method such as electronic density functional theory dft is needed to include the electronic structure and surface chemistry of the electrode into consideration when modeling ruo 2 pseudocapacitance. Chem6085 density functional theory kohnsham energy minimisation the energy is a functional of the density in the kohnsham approach the exact, interacting electrons density is made up from the molecular orbitals mos of the noninteracting electrons so ultimately the energy is a functional of the kohnsham mos. Pdf lattice densityfunctional theory on graphene mari. With firstprinciples density functional theory calculations, we demonstrate that quantum.
Using density functional theory dft methods, we have calculated. Timedependent density functional theory for the charging kinetics of. The two main types of exchangecorrelation functionals used in dft are the local density approximation lda and the generalized gradient approximation gga. Although the dft approach has been successfully applied to model. The idea is to produce supercapacitors with lowcost. Abstract graphene oxide has become an attractive electrode. The energy e stored in a capacitor is directly proportional to its capacitance. Besides, fem calculations, generally described by a con. Quantum capacitance tuned flexible supercapacitor by uvozone. In molecular modeling of supercapacitors, the structure of electrical double layers is.
Mno2 gives superior performance compared to other mno2 polymorphs in surface sensitive applications in supercapacitors and catalysis. Jul 02, 2018 the local diffusion and storage of li, na, and k in hard carbon are probed through density functional theory calculations based on small. In its original formulation, the density functional theory provides the ground state prop. Carbonbased supercapacitors produced by activation of. This is about 10 times higher than the highest expected value of a supercapacitor. The properties of the different energy storage devices are presented in table 1. The compacted density of the facs electrode can be as high as 0. Applications of supercapacitors in electric and hybrid.
Classical density functional theory insights for supercapacitors. The coulomb interaction for a given density interacting the nuclei is very straightforward to compute. The fundamental theorem at the heart of the dft is the hohenbergkohn theorem. Supercapacitors are prized for their high power density. Isbn 9781789233520, eisbn 9781789233537, pdf isbn 97818388727, published 20180627 this edited volume supercapacitors. The enhancement of the quantum capacitance can be contributed to the formation of localized states near dirac point andor shift of fermi level induced by the defects and doping. The journal of chemical physics 2016, 145 20, 204707.
Its applicability ranges from atoms, molecules and solids to nuclei and quantum and classical uids. B each and those at the octahedral sites being nonmagnetic. The mean field density functional theory method proposed by seaton, walton, and quirkel8 is a novel statistical mechanical attempt to extend the accuracy of psd analysis in both the mesopore and micropore range. Density functional theory calculations of the quantum. Supercapacitors have the highest capacitive density available today with densities so high that these capacitors can be used to applications normally reserved for batteries. The power density in a battery has difficulty to reach 200 wkg and is therefore about 20 times smaller than the expected supercapacitor performance. G h distributes uniformly on basal plane of the graphene while in the area near its edge and. The two primary attributes of a capacitor are its energy density and power density. High performance supercapacitor electrodes based on spinel. Firstprinciples simulation of capacitive charging of. Timedependent density functional theory for the charging kinetics of electric double layer containing roomtemperature ionic liquids. Density functional theory is widely used as a tool to calculate ground state energy of electron systems. The fundamentals of density functional theory springerlink.
We discuss the foundations of the nonlocal nldft and quench solid qsdft density functional. How researchers have built a graphenebased supercapacitor with an energy density similar to nickel metal hydride batteries. With firstprinciples density functional theory calculations, we demonstrate that quantum capacitance of graphenebased electrodes can be improved by the ndoping, vacancy defects, and adsorbed transitionmetal atoms. Difference between a conventional capacitor and a supercapacitor 6. The dft methods have found numerous applications for calculating pore size distributions in traditional and newly discovered nanoporous solids. The basic formulations of the dft approach can be found in 62, 63. In doing so, supercapacitors are able to attain greater energy densities while still maintaining the characteristic high power density of conventional capacitors. Density functional theory is one of the most popular and successful quantum mechanical approaches to matter. Density functional theory calculation for quantum capacitance of. Supercapacitor is constructed from two carbon based electrodes, separator between electrodes and electrolyte. Structure of electric double layers in capacitive systems. Solvent effect on the poresize dependence of an organic.
Advancing the supercapacitor materials and technology frontier for improving power quality by prashanth jampani, a. Supercapacitors have low energy density and high power density as compared to batteries, so supercapacitors can be used where there is a sudden power demand. Density functional theory is a powerful method for description of inhomogeneous fluids. Request pdf density functional theory calculation for quantum capacitance of graphene oxide as supercapacitor electrodes graphene. Classical density functional theory for ionic liquids in. Cohen, paula morisanchez, and weitao yang department of chemistry, lens.
They are particularly suited to applications that require energy pulses during short periods of time, e. Hohenberg and kohn, 1964 how to replace the manyelectron problem by an. Pdf classical density functional theory insights for. Pdf density functional theory rakitha beminiwattha. These notes provide an introduction to groundstate density functional theory dft of electronic systems. The density functional theory dft is presently the most successfull and also the most promising approach to compute the electronic structure of matter. We have developed the nonlocal density functional theory nldft model of adsorption on mcm41 22, 23, 29, 40, 43. May 27, 2016 this paper provides the theoretical basis of density functional theory, which is now the most used method for characterizing the surface area of microporous carbons. Controlling porosity in ligninderived nanoporous carbon for supercapacitor applications. Density functional theory provides a powerful tool for computations of the quantum state of atoms, molecules and solids, and of abinitio molecular dynamics. Facile hydrothermal synthesis of mnwo 4 nanorods for nonenzymatic glucose sensing and supercapacitor properties with insights from density functional theory simulations. Understanding the pseudocapacitance of ruo2 from joint density. Supercapacitor capacitance exhibits oscillatory behavior. Modeling materials using density functional theory.
It typically stores 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and. Ruoff, department of mechanical engineering and materials science and engineering program, university of texas at austin, one university station c2200, austin. Supercapacitors are a relatively new energy storage system that provides higher energy density than dielectric capacitors and higher power density than batteries. Again, for portable electronic equipment, the space required for a given storage capacity is an important figure. Density functional theory calculations of the quantum capacitance of graphene oxide as a supercapacitor electrode. Energy densityenhancement mechanism and design principles. Ultrabattery could put a hybrid in every garage by matthew phenix, wired, 25 january 2008.
It is nowadays routinely applied for calculating, e. Quantum capacitance of transition metal and nitrogen codoped graphenes as supercapacitors electrodes. Both nearestneighbour and up to third nearestneighbour hoppings are considered and. Supercapacitors also called ultracapacitors and electric double layer capacitors edlc are capacitors with capacitance values greater than any other capacitor type available today. Capacitance values reaching up to 800 farads in a single standard case size are available. In this paper, we specify a powerful way to boost quantum capacitance of graphenebased electrode materials by density functional theory calculations.
Stateoftheart surface and poresize characterization of the amego was performed by coupling highresolution nitrogen 77. Form of the density functional so whats the density functional actually look like. Enhancement of quantum capacitance by chemical modification. The authors declare no competing financial interest. Comparative electrochemical energy storage performance of. Density functional theory calculations of the quantum capacitance.
A supercapacitor stores energy in electrical double layers at electrodeelectrolyte interfaces. For graphene based supercapacitors in ionic liquids capable of operating up to 4. The quantum capacitance makes relative contributions to the specific. Conventional capacitor has low energy and power density than supercapacitor but supercapacitor has higher power density and lower energy density than battery. In this thesis i will present the concept of cost e cient, paperbased supercapacitors. Supercapacitors can be charged and discharged quickly while the batteries can supply the bulk energy since they can store and deliver larger amount energy over a longer slower period of time. Properties and applications of supercapacitors from the. How combining oldfashioned leadacid batteries and supercapacitors could save on running costs in hybrid cars. Rational design of nanostructured electrode materials for. The electrical conductivity of graphene is much higher than the one of graphitic carbon, and the theoretical surface area of a monolayer is 2620 m2 g 1. The energy density for ultracapacitor is comparable with nickel metal hydride and is higher than nicad and leadacid batteries. Activated graphenebased carbons as supercapacitor electrodes with macro and mesopores taeyoung kim, gyujin jung, seonmi yoo, kwang s. Graphene oxide has become an attractive electrodematerial candidate for supercapacitors thanks to its higher specific capacitance compared to graphene.
Understanding the pseudocapacitance of ruo2 from joint. Density functional theory calculation for quantum capacitance. Advancing the supercapacitor materials and technology. In our recent works, the classical density functional theory cdft was developed and applied to study the electrodeelectrolyte interface behaviors. Characteristics of supercapacitor supercapacitor can not be used for applications in ac circuit such as ripple absorption because it has high internal resistance several hundred m. Dr considers a distribution of adsorption energies that depends on the pore size. Density functional theory plane waves pseudopotentials hohenbergkohn theorem hohenbergkohn theorem hohenberg and kohn proved that the ground state energy of a system of electrons in an external potential vr is the minimum of a universal functional of the electron density e ground min nr. Density functional theory calculations were also carried out to qualitatively support. Supplementary,information,for, optimizing, supercapacitor, electrode, density. A book on using density functional theory to model materials. Supercapacitors are electrochemical energystorage devices that exploit the electrostatic interaction between highsurfacearea nanoporous electrodes and electrolyte ions. Design of supercapacitor electrodes using molecular dynamics.
Here the classical density functional theory is employed to investigate the impurity effects on the microscopic structure and the performance of ionicliquidbased electrical doublelayer. The lecture is intended for a researcher with little or no experience of quantum. Controlling porosity in ligninderived nanoporous carbon for. Understanding the pseudocapacitance of ruo 2 from joint density functional theory cheng zhan and deen jiang department of chemistry, university of california, riverside, ca 92521, usa email. The obtained charge concentration at the gp edges is consistent with recent density functional theory dft and molecular dynamics md results reported by bo et al. Density functional theory calculations for the quantum.
For either measure, the density can be calculated as a quantity per unit mass or per unit volume. A promising tool to describe their physics on a microscopic level is classical density functional theory dft, which can be applied in. Density functional theory model for calculating pore size. The use of supercapacitors is, however, still limited due to their high costs. Supercapacitors are not as volumetrically efficient and are more expensive than batteries but they do have other advantages over batteries making the preferred choice.
Mar 31, 2018 density functional theory calculations of the quantum capacitance of graphene oxide as a supercapacitor electrode ce song school of mathematical sciences, dalian university of technology, no. A firstprinciples roadmap and limits to design efficient. A supercapacitor sc, also called an ultracapacitor, is a highcapacity capacitor with a capacitance value much higher than other capacitors, but with lower voltage limits, that bridges the gap between electrolytic capacitors and rechargeable batteries. It typically stores 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and deliver charge much. Radushkevich and the nonlocal dft density functional theory method 12 ful.
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