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Ti 3 C 2 and Ti 3 CN MXenes were exfoliated from their corresponding MAX phases by electrochemical etching using HBF 4 as the electrolyte. The performance of electrochemically etched MXene as electrodes for Li-ion supercapacitors was studied.
Reliable energy storage at subzero temperatures is crucial for polar and space applications. Nitrogen-doped multiscale porous carbon aerogels deliver 96% capacitance retention at −40 °C and 1.43 Wh L −1 energy density. In conclusion, enhanced nitrogen content and enlarged ion-accessible surface synergistically enable exceptional low-temperature supercapacitor performance.
For electrochemical energy storage, increasing the electrode thickness is an effective approach to achieving higher energy density from a given material. However, this often compromises ion transport, leading to diminished performance. Here, in this study, we present a novel platform for fabricating complex 3D interpenetrating electrode structures via photo-polymerization 3D printing, integrated with computational structural optimization for energy storage. The platform employs an acrylate resin system infused with graphene oxide (GO), enabling high-fidelity printing of optimized porous structures and facilitating efficient electron and ion transport in ultra-thick electrodes. The optimized 3D layouts substantially enhance energy and power densities compared to conventional configurations, ensuring superior material utilization and minimal ohmic losses. Supercapacitors fabricated using this approach achieved an exceptional energy density of 4.7 Wh L−1 at a power density of 1689.0 W L−1, surpassing traditional designs. This work underscores the transformative role of structural optimization in advancing electrochemical performance and establishes a versatile pathway for developing next-generation energy storage systems with exceptional efficiency and functionality.
Ferroelectric materials exhibit the largest dielectric permittivities and piezoelectric responses in nature, making them invaluable in applications from supercapacitors or sensors to actuators or electromechanical transducers. The origin of this behavior is their proximity to phase transitions. However, the largest possible responses are most often not utilized due to the impracticality of using temperature as a control parameter and to operate at phase transitions. This has motivated the design of solid solutions with morphotropic phase boundaries between different polar phases that are tuned by composition and that are weakly dependent on temperature. Thus far, the best piezoelectrics have been achieved in materials with intermediate (bridging or adaptive) phases. But so far, complex chemistry or an intricate microstructure has been required to achieve temperature-independent phase-transition boundaries. Here, we report such a temperature-independent bridging state in thin films of chemically simple BaTiO3. A coexistence among tetragonal, orthorhombic, and their bridging low-symmetry phases are shown to induce continuous vertical polarization rotation, which recreates a smear in-transition state and leads to a giant temperature-independent dielectric response. The current material contains a ferroelectric state that is distinct from those at morphotropic phase boundaries and cannot be considered as ferroelectric crystals. We believe that other materials can be engineered in a similar way to contain a ferroelectric state with gradual change of structure, forming a class of transitional ferroelectrics. Similar mechanisms could be utilized in other materials to design low-power ferroelectrics, piezoelectrics, dielectrics, or shape-memory alloys, as well as efficient electro- and magnetocalorics.
Ionic liquids are widely used as electrolytes in electronic devices in which they are subject to nanoconfinement within nanopores or nanofilms. Because the intrinsic width of an electrical double layer is on the order of several nanometers, nanoconfinement is expected to fundamentally alter the double layer properties. Furthermore, in confined systems, a large portion of the ions are interfacial, e.g., at the electrode interface, leading to significant deviations of electrostatic screening and ion dynamics as compared to bulk properties. In this article, we systematically investigate the interference between electrical double layers for nanoconfined ionic liquids and the resulting influence on the structure, dynamics, and screening behavior. We perform molecular dynamics simulations for the ionic liquids [BMIm + ][BF$^-_4$] and [BMIm + ][PF$^-_6$] confined between two flat electrodes at systematic separation distances between 1.5 nm and 4.5 nm for both conducting and insulating boundary conditions. We find that while ion dynamics is expectedly slower than in the bulk (by ~2 orders of magnitude), there is an unexpected non-linear trend with the confinement length that leads to a local maximum in dynamic rates at ~3.5–4.5 nm confinement. We show that this nonlinear trend is due to the ion correlation that arises from the interference between opposite double layers. We further evaluate confinement effects on the ion structure and capacitance and investigate the influence of electronic polarization of the ionic liquid on the resulting properties. This systematic evaluation of the connection between electrostatic screening and structure and dynamics of ionic liquids in confined systems is important for the fundamental understanding of electrochemical supercapacitors.
Electric double layers are ubiquitous in science and engineering and are of current interest, owing to their applications in the stabilization of colloidal suspensions and as supercapacitors. While the structure and properties of electric double layers in electrolyte solutions near a charged surface are well characterized, there are subtleties in calculating thermodynamic properties from the free energy of a system with charged surfaces. These subtleties arise from the difference in the free energy between systems with constant surface charge and constant surface potential. In this work, we present a systematic, pedagogical framework to properly account for the different specifications on charged bodies in electrolyte solutions. Our approach is fully variational—that is, all free energies, boundary conditions, relevant electrostatic equations, and thermodynamic quantities are systematically derived using variational principles of thermodynamics. We illustrate our approach by considering a simple electrolyte solution between two charged surfaces using the Poisson–Boltzmann theory. Our results highlight the importance of using the proper thermodynamic potential and provide a general framework for calculating thermodynamic properties of electrolyte solutions near charged surfaces. Specifically, we present the calculation of the pressure and the surface tension between two charged surfaces for different boundary conditions, including mixed boundary conditions.
New materials for electrochemical energy storage and conversion are the key to the electrification and sustainable development of our modern societies. Molecular modelling based on the principles of quantum mechanics and statistical mechanics as well as empowered by machine learning techniques can help us to understand, control and design electrochemical energy materials at atomistic precision. Therefore, this roadmap, which is a collection of authoritative opinions, serves as a gateway for both the experts and the beginners to have a quick overview of the current status and corresponding challenges in molecular modelling of electrochemical energy materials for batteries, supercapacitors, CO 2 reduction reaction, and fuel cell applications.
Methods of elucidating the mechanisms of fast-ion conduction in solid-state materials are pivotal for advancements in energy technologies such as batteries, fuel cells, sensors, and supercapacitors. In this study, we examine the ionic conduction pathways in single crystal SrCl2, which is a fast-ion conductor above 900 K, using four-dimensional quasielastic neutron scattering (4D-QENS). We explore both coherent and incoherent neutron scattering at temperatures above the transition temperature into the superionic phase to explore the correlated motion of hopping anions. Refinements of the incoherent QENS yield residence times and jump probabilities between lattice sites in good agreement with previous studies, confirming that ionic hopping along nearest-neighbor directions is the most probable conduction pathway. However, the coherent QENS reveals evidence of de Gennes narrowing, indicating the importance of ionic correlations in the conduction mechanism. This highlights the need for improvements both in the theory of ionic transport in fluorite compounds and the modeling of coherent 4D-QENS in single crystals.
The surfaces of rutile transition-metal oxides (TMO 2 ) are widely investigated for catalysis, photoelectrochemical solar cells, memristors, and supercapacitors, but their structures have remained controversial. Here we employ density functional theory to predict that a universal behavior of metallic TMO 2 surfaces, i.e., the stoichiometric TMO 2 surfaces, exhibit a contrast reversal in simulated scanning tunneling microscopy (STM) images at different scanning biases. The predictions are verified by experimental STM imaging of RuO 2 (110) surfaces and this feature is shown to enable accurate determinations of the TMO 2 (110) surface structures under various conditions. This research provides different insights into the electronic properties of TMO 2 (110) surfaces and offers an effective method to directly map the surface structure and point defects using bias-dependent STM.
An autonomous sensing system for collecting environmental observations in the Arctic region is critical for the estimation and prediction of climate change. Ocean waves are a great source of energy for these sensing systems but there has been limited research done on small-scale energy harvesting applications in the Arctic Ocean (subsea or surface). The available wave energy in the Arctic Ocean is lower than the typical ocean wave energy due to the low wave frequency, height, and operating months. Although the available wave energy depends on the specific location in the Arctic Ocean, the wave height decreases everywhere during the winter (Jan-March) [1]. Our target location in this work is the Beaufort and Chukchi Seas, which are ice covered for about 195 days per year leaving only a few months (June-November) for wave energy harvesting [2]. During these few months, the average wave frequency is 0.2 Hz and the most common wave frequency is around 0.15 Hz. Many energy harvesting methods are unsuitable for use in the Arctic Ocean because of to the cold temperature, low wave frequency, and low wave height. Triboelectric nanogenerators (TENG) are one of the few energy harvesting methods that excel in these conditions. Zhong et al. [3] designed a stacked pendulum-structured TENG for low-frequency ocean wave energy and reported the device generated a peak power density of 11.2 W/m3 under the low wave frequency of 0.2 Hz. The autonomous sensing system we developed for the Arctic Ocean, the Arctic-TENG, is based on a frequency-multiplied cylindrical TENG (FMC-TENG) which is an optimized TENG configuration for Arctic Ocean conditions due to the high power density under low-frequency wave conditions [4]. Figure 1 shows an FMC-TENG with multiple pairs of free-standing triboelectric-layer mode materials (Aluminum and FEP). The mass and magnet attached to the rotor store gravitational potential energy which is released as kinetic energy when the potential energy overcomes the repulsive magnetic force generated by the opposing magnet attached to the stator. This force unbalance triggers a sudden rotation and swinging motion of the mass which increases the angular velocity of the system and therefore enhances the output power of the TENG system. The main components of the Arctic-TENG are a 3D-printed rotor and stator, electric and dielectric material adhesive tape, and bearings. All these materials were cold-soaked and tested at -40 °C in a chest freezer. Both the 3D-printed parts and adhesives were confirmed to have a minimal effect from the cold temperature. Multiple bearings were tested and the starting torque of each one was compared both at room temperature and -40 °C. The bearing with the lowest starting torque at -40 °C was selected for use in the Arctic-TENG. The Arctic-TENG was tested using an out-of-water motor-driven wave simulator (Figure 2). The wave simulator allows for controlled testing at a wave height of 0.2 m and frequencies between 0.1 Hz to 0.5 Hz. This wave simulator was used for both room temperature and -40 °C testing. The Arctic-TENG generated significantly more power at -40 °C compared to room temperature for each frequency tested. The system stored energy in a supercapacitor via a power management circuit, and the amount of energy stored per day was calculated at different wave frequencies. Based on the conditions at the proposed deployment location (days of non-ice-covered ocean and wave frequency), the amount of stored energy per year from Arctic-TENG was calculated to be enough energy for two transmissions every day. Durability testing was completed on the Arctic-TENG at room temperature to determine the lifetime. The rotor of the Arctic-TENG was attached to a DC motor and spun continuously for several millions of cycles without degradation of the electrical output, demonstrating the feasibility for long-term operation.
Carbon aerogels (CA) are known for ultra-low density, very high surface area, fine porous structure, and excellent electrical conductivity. Recent advances in high resolution 3D printing at LLNL enable the manufacturing of complex structured CA electrodes which have been demonstrated in electrolysis, flow battery, and supercapacitor applications. Polymer-electrolyte fuel cells (PEFC) may be an excellent candidate for these materials/methods as designers seek to optimize membrane-electrode assemblies to achieve higher efficiencies. A major challenge to PEFC design is two-phase flow due to water production which causes pore flooding and leads to cell instability and degradation. To mitigate these effects, groups have investigated the creation of liquid specific pathways in the porous layers to alleviate liquid buildup and enhance gas diffusion. While some progress has been made, traditionally manufactured GDLs, which consist of randomly distributed carbon fibers, are limiting. 3D printed CAs are a promising solution as complex macroporous electrode structures can be manufactured out of micro and nano porous filaments with a high level of control. Additionally, the process may allow for the consolidation of multiple layers (MPL, GDL, & flow channels) into a single printed architecture. In this work various CA lattice structures were printed using a direct ink write (DIW) method and liquid breakthrough pressures were measured to demonstrate the ability to tune the water pathways to achieve specific pressure thresholds. Furthermore, a discussion of the prospects for printed CA electrodes in PEFC will focus on material properties, synthesis techniques, and current challenges.
Electrochromic pseudocapacitive transition-metal oxide materials, such as tungsten oxide, which combine fast response, high energy density, and optical effects, can play a significant role as energy storage materials. Here we investigate the electrochemical kinetics of thin films of tungsten oxide, which turn transparent to sky-blue color in the lithiated state due to the reduction of W 6+ to W 5+ . In this study, we investigated the charge density, charge transfer, ion diffusion, and interfacial behavior upon Li + insertion/de-insertion in WO 3 . The electrochromic thin film's pseudocapacitive and electrical double layer mechanism was differentiated based on the power-law. Faradaic diffusion-controlled process dominates over the surface capacitive behavior at scan rates below 40 mV s –1 . These films exhibit an areal charge density of around 100 mC cm –2 and a capacitance of 80 mF cm –2 , superior to most comparable electrochromic materials and supercapacitors. This work combines electrochromics and energy storage properties and provides a fundamental understanding of pseudocapacitive and electrochromic mechanisms in WO 3 .
AC impedance spectroscopy is widely used to evaluate performance limitations in energy storage and conversion devices (e.g., batteries, supercapacitors, and fuel cells). This work shows that integrating the resistive elements in an equivalent circuit as functions of steady-state current enables one to recover overpotentials associated with different processes (e.g., ion migration, charge transfer, and diffusion) in nonlinear electrochemical power supplies. Closed form expressions for diffusion overpotentials are derived using this method for transmissive and reflective boundary conditions and three electrode symmetries (planar, cylindrical, and spherical). Discussion is also extended to macroscopically homogenous porous electrodes which are relevant for most real-world devices. Overall, the approach described herein is a powerful tool to identify rate-limiting steps and guide material/component design.
XRD and XAS were used to characterize the bulk structure, while XPS was used to characterize the surface structure, of commercially obtained nominally K 4 Fe(CN) 6 ·3H 2 O, K 3 Fe(CN) 6 and our synthesized Prussian Blue (PB) material. K 4 Fe(CN) 6 ·3H 2 O was found to consist of a fully hydrated phase, which crystallizes in the monoclinic form and a less hydrated or anhydrous phase which crystallizes in the orthorhombic form. K 3 Fe(CN) 6 was found to consist of the well-established orthorhombic form rather than the monoclinic form. The structure of our synthesized Prussian Blue (PB) was found to be consistent with that reported for (KOH) 0.7 Fe(III) 1.33 Fe(II)(CN) 6 ·4.0H 2 O which crystallizes in the cubic form. XPS and XAS confirmed the presence of ferrous Fe(II) at the surface and bulk levels in K 4 Fe(CN) 6 ·xH 2 O. However, XPS revealed the presence of Fe(II) (~30%) and Fe(III) (~70%) in the surface region of K 3 Fe(CN) 6 while XAS confirmed the presence of mostly Fe(III) at the bulk level. Both XPS and XANES confirmed the presence of Fe(II) and Fe(III) in the surface and bulk regions of PB. We report that this ex situ XAS study will be used to support the analysis of an in situ XAS data collected on a PB containing supercapacitor to understand the mechanistic origin of pseudocapacitance in these devices.
Insights into the dynamics of electrochemical processes are critically needed to improve our fundamental understanding of electron, charge, and mass transfer mechanisms and reaction kinetics that influence a broad range of applications, from the functionality of electrical energy-storage and conversion devices (e.g., batteries, fuel cells, and supercapacitors), to materials degradation issues (e.g., corrosion and oxidation), and materials synthesis (e.g., electrodeposition). To unravel these processes, in situ electrochemical scanning/transmission electron microscopy (ec-S/TEM) was developed to permit detailed site-specific characterization of evolving electrochemical processes that occur at electrode–electrolyte interfaces in their native electrolyte environment, in real time and at high-spatial resolution. This approach utilizes “closed-form” microfabricated electrochemical cells that couple the capability for quantitative electrochemical measurements with high spatial and temporal resolution imaging, spectroscopy, and diffraction. Here, we review the state-of-the-art instrumentation for in situ ec-S/TEM and how this approach has resulted in new observations of electrochemical processes.
The transition from fossil fuels to renewable energy has brought about a rapid increase in the availability of clean electricity. However, electricity generated from sources such as wind and solar are limited to intermittent operation due to daily and seasonal variation. One solution is to utilize electrochemical devices in energy storage and electrochemical manufacturing applications, where they can harness surplus energy and decarbonize chemical industries traditionally reliant on petrochemical feedstocks. Managing the growing prevalence of renewable energy underscores the importance of developing and scaling up these technologies, which can in turn facilitate the achievement of carbon emission reduction commitments of companies and developed economies. Likewise, the electrification of transport creates an increasing need for energy-dense electrochemical energy storage devices such as batteries and supercapacitors. Naturally, simulation tools are required to assist in the design of efficient and industrial-scale electrochemical devices.
This work provides an overview and compares key operating characteristics of select energy storage technologies. This work explores how these storage technologies may be used to improve the flexibility and reliability of power systems given their technical characteristics. The report covers various electrochemical (lithium-ion, lead-acid, flow, sodium-sulfur), chemical (hydrogen), mechanical (pumped hydro storage, compressed air energy storage, flywheels, gravity) and electrical (supercapacitors) storage mediums.
Partnering additive manufacturing (3D printing) with functional nanomaterial-based inks has the potential to push the properties and performance of advanced materials beyond previous capabilities. This is particularly true in energy and environmental applications. Graphene, 2D materials, and ceramic-based inks, when coupled with 3D printing technologies like Direct Ink Writing (DIW), also called “robocasting,” have shown promise to greatly enhance the performance of batteries, supercapacitors, reactors, and separator devices. Robocasting enables the printing of large-scale electrodes for energy applications with micron resolution by using high concentration viscous inks.