Pseudocapacitors are energy-storage devices characterized by fast and reversible redox reactions that enable them to store large amounts of electrical energy at high rates. We simulate the response of pseudocapacitive electrodes under realistic conditions to identify the microscopic factors that determine their performance, focusing on ruthenia (RuO2) as a prototypical electrode material. Electronic-structure methods are used together with a self-consistent continuum solvation (SCCS) model to build a complete dataset of free energies as the surface of the charged electrode is gradually covered with protons under applied voltage. The resulting dataset is exploited to compute hydrogen-adsorption isotherms and charge-voltage responses by means of grand-canonical sampling, finding close agreement with experimental voltammetry. These simulations reveal that small changes on the order of 5 μF/cm2 in the intrinsic double-layer capacitance of the electrode-electrolyte interface can induce variations of up to 40 μF/cm2 in the overall pseudocapacitance.
Ni(OH)2 nanocrystals grown on graphene sheets with various degrees of oxidation are investigated as electrochemical pseudocapacitor materials for potential energy storage applications. Single-crystalline Ni(OH)2 hexagonal nanoplates directly grown on lightly-oxidized, electrically-conducting graphene sheets (GS) exhibit a high specific capacitance of ~1335F/g at a charge and discharge current density of 2.8A/g and ~953F/g at 45.7A/g with excellent cycling ability. The high specific capacitance and remarkable rate capability are promising for applications in supercapacitors with both high energ…
Cobalt carbonate hydroxide (CCH) is a pseudocapacitive material with remarkably high capacitance and cycle stability. Previously, it was reported that CCH pseudocapacitive materials are orthorhombic in nature. Recent structural characterization has revealed that they are hexagonal in nature; however, their H positions still remain unclear. In this work, we carried out first-principles simulations to identify the H positions. Through the simulations, we could consider various fundamental deprotonation reactions inside the crystal and computationally evaluate the electromotive forces (EMF) of th…
With the rapid development of economy, the consumption of fossil fuels, and the increasing environment pollution, there is in urgent need of seeking clean and renewable energy sources, as well as highly efficient and low-cost energy storage technologies. Concerning electrochemically active materials, transition metal oxides (TMOs) are regarded as the most promising candidates for the next generation SCs and have been widely reported. Therefore, in this review, we mainly pay attention to TMOs with excellent electrochemical performance. This review is divided into four parts: (a) the background …
MXene transition-metal carbides and nitrides are of growing interest for energy storage applications. These compounds are especially promising for use as pseudocapacitive electrodes due to their ability to convert energy electrochemically at fast rates. Using voltage-dependent cluster expansion models, we predict the charge storage performance of MXene pseudocapacitors for a range of electrode compositions. $M_3C_2O_2$ electrodes based on group-VI transition metals have up to 80% larger areal energy densities than prototypical titanium-based ( e.g. $Ti_3C_2O_2$) MXene electrodes. We attribute …
Supercapacitor electrodes fabricated from a nanocomposite consisting of multiwall carbon nanotubes and titanium oxide nanoparticles were characterized electrochemically. Conventional electrochemical characterizations cyclic voltammetry and galvanostatic charge-discharge in a lithium-based electrolyte gave a specific capacitance of 345 F/g at a current density of 0.1 A/g. New electrochemical characterization techniques that allow one to obtain the peak capacitance associated with intercalation and to distinguish between electrostatic and faradaic charge storage are described and applied to the …
Here, we correlate the nanoscale morphology and chemical composition of solid electrolyte interphases (SEI) with the electrochemical property of graphite-based composite electrodes. Using electrochemical strain microscopy (ESM) and X-ray photoelectron spectroscopy (XPS), changes of chemical composition and morphology (Li and F distribution) in SEI layers on the electrodes as a function of solid electrolyte contents are analyzed. As a result, we find a strong correlation between morphological variations on the electrode, Li and F distribution in SEI layer, and Coulomb efficiency. This correlati…
Electrochemical strains are a ubiquitous feature of solid state ionic devices ranging from ion batteries and fuel cells to electroresistive and memristive memories. Recently, we proposed a scanning probe microscopy (SPM) based approach, referred as electrochemical strain microscopy (ESM), for probing local ionic flows and electrochemical reactions in solids based on bias-strain coupling. In ESM, the sharp SPM tip concentrates the electric field in a small (10-50 nm) region of material, inducing interfacial electrochemical processes and ionic flows. The resultant electrochemical strains are det…
Electropolymerization of anilinium hydrochloride was carried out on platinum plate electrode in a protic medium by cyclic voltammetry. The effects on the electrodeposition of the sweep rate, monomer concentration, pH of the medium and electrode nature are discussed.
A combination of experimental measurements and numerical simulations are used to characterize the mechanical and electrochemical response of thin film amorphous Si electrodes during cyclic lithiation. Parameters extracted from the experiment include the variation of elastic modulus and the flow stress as functions of Li concentration; the strain rate sensitivity; the diffusion coefficient for Li transport in the electrode; the free energy of mixing as a function of Li concentration in the electrode; the exchange current density for the Lithium insertion reaction; as well as reaction rates and …
This work explores the use of joint density-functional theory, a new form of density-functional theory for the ab initio description of electronic systems in thermodynamic equilibrium with a liquid environment, to describe electrochemical systems. After reviewing the physics of the underlying fundamental electrochemical concepts, we identify the mapping between commonly measured electrochemical observables and microscopically computable quantities within an, in principle, exact theoretical framework. We then introduce a simple, computationally efficient approximate functional which we find to …
Vertical graphene nanosheets (VGN) grown as controlled porous network are studied and demonstrated as a promising electrode material for supercapacitors. The VGN synthesized by microwave plasma enhanced chemical vapor deposition using CH4/Ar gas mixture as precursor are considered for electrochemical performance in Na2SO4, KOH, and H2SO4 to delineate the electrolyte effect. Among the electrolytes, H2SO4 exhibited excellent specific areal capacitance (188 microfarad/cm2) and good capacitance retention (96.8%). No significant change is observed in impedance spectra even after 200 cycles. An elec…
We present results of an approach to incorporate redox-active manganese oxide into the 3-dimensional porous structure of carbon xerogels under self-limiting electroless conditions. By varying the structure of the carbon backbone, we found that deposition of manganese oxide preferably takes place on the external surface area of the carbon xerogels. From our detailed analysis we conclude that 3-dimensional carbon xerogels with particle and pore sizes ranging from 10 to 20 nm and low manganese oxide precursor concentration combined with long deposition times are beneficial for fast operating pseu…
Herein we report on a detailed investigation of the irreversible capacity in the first cycle of pyrolytic graphite electrodes in aluminum batteries employing 1-ethyl-3-methylimidazolium chloride:aluminum trichloride (EMIMCl:AlCl3) as electrolyte. The reaction mechanism, involving the intercalation of AlCl4 in graphite, has been fully characterized by correlating the micro/nanostructural modification to the electrochemical performance. To achieve this aim a combination of X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and computed tomography (CT) has been used. The reported result…
Smoothed Boundary Method Framework for Electrochemical Simulation of Li-ion Battery Cathode with Complex Microstructure: Model, Formulation and Parameterization
Composite cathode coatings made of a high energy density layered oxide (Li1.2Ni0.15Mn0.55Co0.1O2, theoretical capacity ~377 mAh/g), polyvinylidene fluoride (PVdF) binder, and electron-conduction additives, were bonded to an elastic substrate. An electrochemical cell, built by pairing the cathode with a capacity-matched graphite anode, was electrochemically cycled and the real-time average stress evolution in the cathode coating was measured using a substrate-curvature technique. Features in the stress evolution profile showed correlations with phase changes in the oxide, thus yielding data com…
We review recent ab initio molecular dynamics studies of electrode/electrolyte interfaces in lithium ion batteries. Our goals are to introduce experimentalists to simulation techniques applicable to models which are arguably most faithful to experimental conditions so far, and to emphasize to theorists that the inherently interdisciplinary nature of this subject requires bridging the gap between solid and liquid state perspectives. We consider liquid ethylene carbonate (EC) decomposition on lithium intercalated graphite, lithium metal, oxide-coated graphite, and spinel manganese oxide surfaces…
An in situ study of stress evolution and mechanical behavior of germanium as a lithium-ion battery electrode material is presented. Thin films of germanium are cycled in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1M LiPF6 in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt. %) as electrolyte. Real-time stress evolution in the germanium thin-film electrodes during electrochemical lithiation/delithiation is measured by monitoring the substrate curvature using the multi-beam optical sensing method. Upon lithiation a-Ge under…
We report in situ measurements of stress evolution in a silicon thin-film electrode during electrochemical lithiation and delithiation by using the Multi-beam Optical Sensor (MOS) technique. Upon lithiation, due to substrate constraint, the silicon electrode initially undergoes elastic deformation, resulting in rapid rise of compressive stress. The electrode begins to deform plastically at a compressive stress of ca. -1.75 GPa; subsequent lithiation results in continued plastic strain, dissipating mechanical energy. Upon delithiation, the electrode first undergoes elastic straining in the oppo…
To study the electrochemical reaction on surfaces, phase interfaces, and crack surfaces in the lithium ion battery electrode particles, a phase-field model is developed, which describes fracture in large strains and anisotropic Cahn-Hilliard-Reaction. Thereby the concentration-dependency of the elastic properties and the anisotropy of diffusivity are also considered. The implementation in 3D is carried out by isogeometric finite element methods in order to treat the high order terms in a straightforward sense. The electrochemical reaction is modeled through a modified Butler-Volmer equation to…
This report presents some of the key laboratory electrochemical battery testing methods that are used in fuel cell research. Methods such as voltammetry, chronoamperometry, chronopotentiometry, and electrochemical impedance spectroscopy are of major importance. All the electrochemical corrosion tests are performed through a tri-electrode polarization cell setup containing a reference electrode, a counter electrode, and the working electrode (metal sample of interest) in an electrolyte solution. All three electrodes are connected to a potentiostat. Corrosion of metal occurs through an oxidation…
A better understanding of interfacial mechanisms is needed to improve the performances of electrochemical devices. Yet, simulating an electrode surface at fixed electrolyte composition remains a challenge. Here we apply a finite electric field to a single electrode held at constant potential and in contact with an aqueous ionic solution, using classical molecular dynamics. The polarization yields two electrochemical interfaces on opposite sides of the same metal slab. While the net charge on one electrode surface is the opposite of the net charge on the other, maintaining overall charge neutra…
Based on the reported ion migration under electric field in hybrid lead halide perovskites we have developed a bright, light emitting electrochemical cell with CH3NH3PbBr3 single crystals directly grown on vertically aligned carbon nanotube (VACNT) forests as contact electrodes. Under the applied electric field, charged ions in the crystal drift and accumulate in the vicinity of the electrodes, resulting in an in operando formed p-i-n heterojunction. The decreased interface energy barrier and the strong charge injection due to the CNT tip enhanced electric field, result in a bright green light…
Electrochemical impedance spectra for battery electrodes are usually interpreted using models that assume isotropic active particles, having uniform current density and symmetric diffusivities. While this can be reasonable for amorphous or polycrystalline materials with randomly oriented grains, modern electrode materials increasingly consist of highly anisotropic, single-crystalline, nanoparticles, with different impedance characteristics. In this paper, analytical expressions are derived for the impedance of anisotropic particles with tensorial diffusivities and orientation-dependent surface…
Herein, we report a improved method for the physical grafting of 1-nitropyrene (Pyr-NO2) onto highly graphitized carbon onion. This is achieved through a lowering of the onset potential of the pyrene polymerization via in situ reduction of the NO2 group. The additional redox activity pertaining to the reduced NO2 enables exceeding the faradaic capacity which is associated with the p-doping of the grafted pyrene backbone, as observed for pyrene, 1-aminopyrene, and unreduced Pyr- NO2. Theoretical calculations demonstrate the charge transfer and binding enthalpy capabilities of Pyr-NO2, which are…
The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface elec- trification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surf…
Supercapacitors, based on the fast ion transportation, are specialized to provide high power, long stability, and efficient energy storage with highly porous electrode materials. However, their low energy density and specific capacitance prevent them from many applications that require long duration. Using a scalable nanoporous graphene synthesis method involving a simple annealing process in hydrogen, here we show graphene supercapacitors capable of achieving a high energy density comparable to what Li-ion batteries can offer, but a much higher power density. Ultra-high specific gravimetric a…
We synthesized the pure and co-doped titanium dioxide (TiO$_2$) electrodes via spin coating. We examined the optical and electronic properties of as-prepared thin film electrodes with co-doping of transition metals and non-metals. The co-doping of Cu, Zn, and N increase the absorption of the radiation in the visible region. The doping leads to the formation of defect states in the electrodes. In this article, we have studied the carrier kinetics in pristine and co-doped TiO2 electrodes. To study the role of dopants in carrier transport of the synthesized TiO2 based electrodes, the electrochemi…
Electrochemical energy systems rely on particulate porous electrodes to store or convert energies. While the three-dimensional porous structures were introduced to maximize the interfacial area for better overall performance of the system, spatiotemporal heterogeneities arose from materials thermodynamics localize the charge transfer processes onto a limited portion of the available interfaces. Here, we demonstrate a simple but precision method that can directly track and analyze the operando (i.e. local and reacting) interfaces at the mesoscale in a practical graphite porous electrode to obta…
Characterizing electrochemical energy conversion devices during operation is an important strategy for correlating device performance with the properties of cell materials under real operating conditions. While operando characterization has been used extensively for low temperature electrochemical cells, these techniques remain challenging for solid oxide electrochemical cells due to the high temperatures and reactive gas atmospheres these cells require. Operando X-ray diffraction measurements of solid oxide electrochemical cells could detect changes in the crystal structure of the cell materi…
Three Cu(II/I)-phenanthroline and Cu(II/I)-bipyridine redox mediators are studied on various electrodes and in variety of electrolyte solutions using cyclic voltammetry and impedance spectroscopy on symmetrical dummy cells.
Using Density functional theory (DFT) in conjunction with a solvation model we have investigated the phenomenon of eletrode-electrolyte interaction at the electrode surface and its consequences on the electrochemical properties like the charge storage and total capacitance of doped and substituted oxygen functionalised Ti$_{3}$C$_{2}$ supercapcitor electrode. We have studied nitrogen doped, nitrogen substituted and molybdenum substituted Mxenes in acidic electrolyte H$_{2}$SO$_{4}$ solution. By considering nitrogen doping at different sites, we found that the greatest capacitance is obtained f…
An in situ study of deformation, fracture, and fatigue behavior of silicon as a lithium-ion battery electrode material is presented. Thin films (100-200 nm) of silicon are cycled in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1M lithium hexafluorophosphate in ethylene carbonate, diethylene carbonate, dimethyl carbonate solution (1:1:1, wt.%) as electrolyte. Stress evolution in the Si thin-film electrodes during electrochemical lithiation and delithiation is measured by monitoring the substrate curvature using the multi-beam optical sensing method. The…
Energy demands of modern society require efficient means of energy conversion and storage. Nanocarbons have been identified as versatile materials which combine many desirable properties, allowing them to be used in electrochemical power sources, from electrochemical capacitors to fuel cells. Efficient production of nanocarbons requires innovative and scalable approaches which allow for tuning of their physical and chemical properties. Carbonization of polymeric nanostructures has been demonstrated as a promising approach for production of high-performance nanocarbons with desired morphology a…
Electrochemical kinetics at electrode-electrolyte interfaces are crucial to understand high-rate behavior of energy storage devices. Phase transformation of electrodes is typically treated under equilibrium thermodynamic conditions, while realistic operation is at finite rates. Analyzing phase transformations under nonequilibrium conditions requires integrating nonlinear electrochemical kinetic models with thermodynamic models. This had only previously been demonstrated for Butler-Volmer kinetics, where it can be done analytically. In this work, we develop a kinetic modeling package in the Jul…
To pursuit high electrochemical performance of supercapacitors based on Faradaic charge-transfer with redox reaction or absorption/desorption effect, the intercalation efficiency of electrolyte ions into electrode materials is a crucial prerequisite to surpass the pure surface capacity with extra bulk contribution. Here we report layered barium transition metal fluorides, BaMF4 (M = Mn, Co, Ni) to be a series of new electrode materials applied in standard three-electrode configuration. Benefiting from the efficient immersing of electrolyte ions, these materials own prominent specific capacitan…
Two-dimensional transition metal-dichalcogenides are emerging as efficient and cost-effective electrocatalysts for hydrogen evolution reaction (HER). However, only the edge sites of their trigonal prismatic phase show HER-electrocatalytic properties, while the basal plane, which is absent of defective/unsaturated sites, is inactive. Here, we tackle the key challenge that is increasing the number of electrocatalytic sites by designing and engineering heterostructures composed of single-/few-layer MoSe2 flakes and carbon nanomaterials (graphene or single-wall carbon nanotubes (SWNTs)) produced b…
Macroscopic ensembles of nanocarbons, such as fibres of carbon nanotubes (CNT), are characterised by a complex hierarchical structure combining coherent crystalline regions with a large porosity arising from imperfect packing of the large rigid building blocks. Such structure is at the centre of a wide range of charge storage and transfer processes when CNT fibres are used as electrodes and/or current collectors. This work introduces a method based on wide and small-angle X-ray scattering (WAXS/SAXS) to obtain structural descriptors of CNT fibres and which enables in situ characterisation duri…
The ab initio simulation of charged interfaces in the framework of density functional theory (DFT) is heavily employed for the study of electrochemical energy conversion processes. The capacitance is the primary descriptor for the response of the electrochemical interface. It is essentially equal to the inverse of the energy curvature as a function of electron number, and as such there appears a conflict with the fundamental principle of piecewise linearity in DFT that requires the energy curvature to be zero at fractional electron numbers, i.e. almost everywhere. To resolve this conflict, we …
Ab initio modeling of electrochemical systems is becoming a key tool for understanding and predicting electrochemical behavior. Development and careful benchmarking of computational electrochemical methods are essential to ensure their accuracy. Here, using charging curves for an electrode in the presence of an inert aqueous electrolyte, we demonstrate that most continuum models, which are parameterized and benchmarked for molecules, anions, and cations in solution, undersolvate metal surfaces, and underestimate the surface charge as a function of applied potential. We examine features of the …
Recycling of beta-Li3PS4-based all-solid-state Li-ion batteries: Interactions of electrode materials and electrolyte in a dissolution-based separation process
Graphene sponge electrodes were employed for chlorine-free inactivation of Escherichia coli from low conductivity water. The nitrogen-doped reduced graphene oxide (NRGO) sponge anode bearing more positive charge achieved complete E. coli inactivation (i.e., 5 log removal) in the anode-cathode configuration at 115 A m-2, versus 2.6 log removal using boron-doped reduced graphene oxide sponge anode. The bacteria were mainly inactivated via electrosorption and electroporation, as confirmed by the scanning electron microscopy. Storage of the electrochemically treated samples revealed further killin…
Ionic liquids are widely used as electrolytes in electrochemical devices. In this context, many experimental and theoretical approaches have been recently developed for characterizing their interface with electrodes. In this perspective article, we review the most recent advances in the field of computer simulations (mainly molecular dynamics). A methodology for simulating electrodes at constant electrical potential is presented. Several types of electrode geometries have been investigated by many groups in order to model planar, corrugated and porous materials and we summarize the results obt…
The electrochemical deposition of ZnO hierarchical nanostructures directly from PHEMA hydrogel coated electrodes has been successfully demonstrated. A variety of hierarchical ZnO nanostructures, including porous nanoflakes, nanosheets and nanopillar arrays were fabricated directly from the PHEMA hydrogel coated electrodes. Hybrid ZnO-hydrogel composite films were formed with low zinc concentration and short electrodeposition time. A dual-layer structure consisting of a ZnO/polymer and pure ZnO layer was obtained with zinc concentration above 0.01 M. SEM observations and XPS depth profiling wer…
A continuous CO2 vapor-fed electrochemical cell prototype that performs CO2R with high faradaic efficiency for desired carbon products for up to 72 hours of operation is presented. The cell design facilitates a flow through configuration, capitalizing on gas diffusion electrode (GDE) and membrane electrode architecture (MEA) without requiring a catholyte. We demonstrate stable performance and design adaptability by incorporating various CO2R catalysts and membranes into the cell, investigating lifetime performance and selectivity under established experimental conditions. With an Ag foil and P…
Identifying overpotential components of electrochemical systems enables quantitative analysis of polarization contributions of kinetic processes under practical operating conditions. However, the inherently coupled kinetic processes lead to an enormous challenge in measuring individual overpotentials, particularly in composite electrodes of lithium-ion batteries. Herein, the full decomposition of electrode overpotential is realized by the collaboration of single-layer structured particle electrode (SLPE) constructions and time-resolved potential measurements, explicitly revealing the evolution…
Pilot study of electrochemical reduction of selected nucleotides and double-stranded DNA at pristine micro-/ultrananocrystalline boron-doped diamond electrodes at very negative potentials
