Ion Energy Research Articles

Large scale atomistic and quantum mechanical study of Na+ ion transport in liquid electrolytes for batteries

Lithium–ion batteries (LIBs) have long dominated energy storage markets due to their high energy density and reliability. However, concerns over lithium scarcity and geographic distribution necessitate alternatives. Sodium-ion batteries (SIBs) offer a promising solution due to sodium's abundance, cost-effectiveness, and favorable electrochemical properties. This study investigates Na+ ion transport, aggregation, and performance in various organic electrolytes using molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The electrolytes studied include ethylene carbonate (EC), propylene carbonate (PC), dimethoxyethane (DME), and dimethyl carbonate (DMC) at 320 K. We focused on conductivity, diffusivity, and survival probability of Na+ ions at different salt concentrations. Furthermore, the solvation structure and the binding energy of ions in the electrolytes are thoroughly analyzed. Key findings reveal that at 2 M salt concentration, Na+ ion diffusivity and ionic conductivity follow the order EC>PC>DME>DMC. Increasing salt concentration decreases self–diffusion coefficients of Na+ and PF6− ions across all electrolytes, affecting conductivity. EC shows the highest ionic conductivity at both 1 M and 2 M salt concentrations. These insights suggest that a 2 M NaPF6 concentration in EC optimizes ionic conductivity, making it ideal for high–performance SIBs. This study provides crucial understanding for optimizing electrolytes in SIBs, advancing their development for scalable energy storage solutions.

Variability of Earth’s ionospheric outflow in response to the dynamic terrestrial exosphere

The most abundant neutral constituent in the exospheric region (i.e., beyond ≈ 500 km altitude) is the atomic hydrogen (H); however, its density distributions predicted by physics-based models have been challenged by satellite-based observations of its far ultraviolet emissions. This discrepancy may impact magnetospheric ions’ densities and velocities since numerous chemistry and ion-neutral coupling interactions rely sensitively on the underlying neutral hydrogen population. The Polar Wind Outflow Model a first-principled model for relevant ion species in the high-latitude ionosphere, is employed to investigate the role of neutral H on the ionospheric outflow. Specifically, variability in the outflow of ionospheric H+, He+, N+, and O+ as a response to systematic enhancement and depletion of H number densities were simulated. The altitude-dependent ion density and energy partition profiles vary with neutral H density, solar activities, and ion species. These findings suggest that the exosphere plays a crucial role in controlling the production and loss of ions through ionospheric chemistry, as well as the energy contributions by altering ion-neutral-electron collisions and the ambipolar electric field to the high-latitude ionospheric outflow. As a result, the escape rates of the ionospheric outflow are directly associated with exospheric distributions. This work potentially helps understand the dominant mechanisms of atmospheric escape, particularly during a hydrogen-rich early Earth’s and exoplanet’s atmosphere, which is known to play a significant role in understanding the evolution of Earth’s atmosphere.

Effect of the alkyl chain length of α,ω-dichloroalkane on the Gibbs energy of transfer for functional groups.

Ion-transfer reactions of alkyl and perfluoroalkyl carboxylate ions (CH3(CH2)n-2COO- with n = 8-12 and CF3(CF2)n-2COO- with n = 3-9) were investigated at the polarized Cl-(CH2)m-Cl with m = 2, 4, 6, and 8 (O) | water (W) interface to evaluate the effects of n and m on the solvation energy of the ions, as well as on their methylene and terminal groups. These ions exhibited reversible or quasi-reversible voltammetric waves due to their transfer across the O | W interfaces, enabling the determination of formal potentials and formal Gibbs transfer energies from O to W, . The values for CH3(CH2)n-2COO- and CF3(CF2)n-2COO- increased linearly with n, allowing the estimation of for methylene and difluoromethylene groups, (CH2) and (CF2), and for their terminal groups, (COO- + CH3) and (COO- + CF3). Whereas the (CH2) and (CF2) hardly changed with the variation in m, the (COO- + CH3) and (COO- + CF3) decreased noticeably. These results suggest that the solvation energy for ions in Cl-(CH2)m-Cl increases with m, regardless of hydrophilic or lipophilic nature of the ions. Based on these findings, the advantage of using Cl-(CH2)m-Cl with a large m as a non-aqueous solvent for ion-transfer voltammetry was discussed.

Adjustable ion energy barrier for reliable memristive neuromorphic systems

Adjustable ion energy barrier for reliable memristive neuromorphic systems

Inhibiting the zinc anodes corrosion to achieve ultra-stable high temperature aqueous zinc-ion hybrid supercapacitors

The corrosion of zinc anode significantly undermines the stability of aqueous zinc-based energy storage devices (ZnESDs), potentially leading to cell failure even explosions. In this study, we mixed a high concentration electrolyte (21 m LiTFSI) with a conventional 2 m Zn(OTF)2 electrolyte to highly reduce the activity of solvent water, which can greatly suppress the corrosion of zinc anode at room temperature and high temperatures. We systematically studied the phenomenon of ZnWiS inhibiting zinc anode corrosion at different temperatures and investigated its principle through experiments and theoretical calculations. As a result, the Zn||Zn symmetric cells demonstrated remarkable stability, sustaining over 3642 h at room temperature and over 112 h at 80 °C. Moreover, the as assembled aqueous zinc ion hybrid supercapacitors (ZHSC) also exhibited excellent cycling stability for over 5220 h at room temperature and over 165 h at 80 °C. In contrast, ZHSC assembled with 2 m Zn(OTF)2 can only cycle 80 h at room temperature, and 9 h at 80 °C. These findings confirm that reducing water activity in the electrolyte effectively contributes to achieving highly stable aqueous ZnESDs, and the universality of this strategy offering promise for its application in various aqueous metal ion energy storage devices.

Mid-infrared Measurements of Ion-irradiated Carbonaceous Meteorites: How to Better Detect Space Weathering Effects

Remote sensing study of asteroids will soon enter a new era with an increasing amount of data available thanks to the JWST, especially in the mid-infrared (MIR) range that allows identification of mineral species. It will then be possible to establish a taxonomy, as is currently available in the visible–near-infrared range, based on MIR spectral parameters. It had been previously shown that the MIR range is very sensitive to space weathering (SpWe) effects. Thus, it is crucial to determine which spectral changes are involved to disentangle initial composition from surface aging and provide tools to interpret future remote sensing data of asteroids. We present here MIR measurements of a wide variety of ion-irradiated carbonaceous chondrites as a simulation of the solar wind SpWe component. We evaluate several parameters (the Christiansen feature and Reststrahlen band positions, the width of the main Si–O band) and test different measurement conditions (ion energy and geometry of observation). We highlight a dependency of the spectral changes with the initial composition, as hydrated samples are more affected than anhydrous ones. We confirm the role of the geometry in the detection of SpWe effects as already shown in the near-infrared, with a competition effect between the depth probed by photons and the implantation depth of ions (function of the energy used). We will discuss the results in the framework of future observations and Ryugu’s and Bennu’s samples studied in the laboratory.

A unified global model accompanied with a voltage and current sensor for low-pressure capacitively coupled RF discharge

A global model (GM) assumes ion energy ( ε ) on the electrode equals the time-averaged sheath voltage ( Vshtt ). However, using particle-in-cell simulation, we found that ε differs from Vshtt. We propose a unified global model (UGM) that calculates ε and collisional energy losses of ions by employing plasma circuit and sheath models, accompanied by a voltage and current sensor. We compared the results of the UGM with the experimental measurements and the results revealed that UGM is closer to the experiment than GM. UGM shows a linear relationship with the experiment, indicating that the UGM is applicable for plasma monitoring.

Plasma-enhanced atomic layer deposition of silicon nitride thin films with different substrate biasing using Diiodosilane precursor

In this work, we report on Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of SiNx films using Diiodosilane (DIS) precursor and N2-H2 plasma. Systematic studies as a function of DIS dosing time, plasma duration, plasma composition and deposition temperature are investigated. The material properties have been studied using X-ray photoelectron spectroscopy (XPS), X-Ray Reflectometry (XRR), Atomic Force Microscopy (AFM) and High-Resolution Transmission Electron Microscopy (HR-TEM). The optimal deposition parameters for achieving high-quality SiNx with a high growth per cycle (GPC) are first determined. We show that DIS offers a wide temperature window for SiNx deposition starting from 110 °C up to 300 °C, paving the way for a large choice of SiN-based applications. The impact of substrate biasing on SiNx film deposition and properties is also investigated. We show that high ion energies during the nitridation step can cause surface damage and void formation, thus affecting the SiNx quality. Overall, these results highlight the importance of this novel precursor for growing SiNx using PE-ALD and the possible swapping of the material properties by fine control of the substrate biasing, which can help to go far beyond the existing SiNx limitations.

The effect of chemical doping on the lithiation processes of the crystalline Si anode ‒ A first-principles study.

We employed first-principles calculations to investigate the effect of chemical doping on the lithiation kinetics and dynamic properties of the c-Si anode. Our abinitio molecular dynamics simulations reveal that phosphorous/arsenic doping can greatly enhance the lithiation kinetics of c-Si, whereas boron doping is unable to produce such an improvement. Our calculations also show that boron doping could enhance Li insertion into c-Si, but phosphorous/arsenic doping tends to increase the insertion energy of Li ions. Although the migration energy barriers of Li ions may slightly increase (decrease) in the boron-(phosphorus-/arsenic-)doped c-Si, these changes were only effective within the range of the nearest-neighbor distance from dopants. Furthermore, it was found that the phosphorus-/arsenic-doped Si can be more ductile and can more easily undergo plastic deformation upon lithiation, while the c-Si matrix becomes more brittle and stiffer when doped with boron. Our simulation results also demonstrate that phosphorous- and arsenic-doping can effectively speed up the Li-induced structural amorphization of c-Si while boron doping appears to severely slow it down. These findings unambiguously indicate that the induced mechanical softening of the c-Si bond network can be the primary factor that leads to the enhanced lithiation kinetics in the n-type doped c-Si anodes.

Effect of sputtering power and thickness ratios on the materials properties of Cu–W and Cu–Cr bilayer thin films using high power impulse magnetron and DC magnetron sputtering

This study investigates the influence of Cu thickness ratios on the structural, morphological, and mechanical properties of sputtered Cu–W and Cu–Cr bilayer thin films. Employing high power impulse magnetron sputtering (HiPIMS), five distinct thickness ratios of 1:3, 3:5, 1:1, 5:3, and 3:1 were analyzed and compared to bilayer films developed using direct current magnetron sputtering (DCMS). The microstructural and surface characteristics of these films were evaluated using x-ray diffraction (XRD), atomic force microscopy, and scanning electron microscopy. Electrical properties were measured using a four-point probe, while mechanical properties were assessed through nanoindentation. Results reveal that increasing Cu thickness in Cu–W and Cu–Cr bilayers inversely affects hardness, grain size, and roughness, highlighting the influence of thickness ratios on film properties. Films with a higher Cu thickness ratio in both Cu–W and Cu–Cr bilayer systems deposited by HiPIMS exhibited lower hardness, smaller grain size, and reduced average roughness. Cross-sectional analysis and XRD confirmed the impact of thickness ratio on crystal phase and microstructure, indicating smoother columnar structures. Specifically, the HiPIMS-deposited Cu–Cr 3-1 film exhibited the lowest resistivity, at 4.77 μΩ cm, and hardness, measuring 8.26 GPa. Moreover, the 1:1 ratio films of Cu–W and Cu–Cr demonstrated hardness values of 13.81 and 11.37 GPa, respectively, which were 1.39 times higher than the films grown by DCMS. Additionally, variations in the bilayer thickness ratio significantly affected the electrical properties of the films. The enhanced properties of HiPIMS films are attributed to the higher peak power density of the target, leading to increased ion energy and deposition of dense grain structures.

Single Event Effects in 3.3 kV 4H-SiC MOSFETs due to MeV Ion Impact

In this work, MeV alpha particles generated from an accelerator are used to study single event breakdown (SEB) in 4H-SiC MOSFET samples, rated at 3.3 kV. The samples are exposed to bursts of alpha particles under reverse bias conditions to investigate the SEB sensitivity to ion energy and reverse bias. The energies of alpha particles are chosen to reach different depths in the drift region of the MOSFET devices, and also to penetrate the whole drift region. Forward and reverse characteristics are measured after each exposure, as long as no failures occur, to ensure that the device performance is maintained. The measurements show that no significant effects are observed on the drain-source leakage current, while minor effects on gate behavior can be seen as a function of accumulated fluence. Furthermore, SEB can only be triggered with a reverse bias larger than, or equal to 3 kV. A standard MOSFET cell with a similar rated voltage is also simulated in Sentaurus TCAD to study these effects, using two different models for the incident ion-induced ionization: the Alpha Particle and the Heavy Ion model. Simulations show that the Alpha Particle model cannot induce any device failures even with a 3.5 kV reverse bias, while it is possible to trigger a failure by the Heavy Ion model, where the ionization can be selected. Carrier plasma and internal electric field distributions of the two models are plotted and compared, showing that device failures triggered by a heavy ion are related to the hole injection at epi-substrate interface, in which linear energy transfer (LET) of the particle plays an important role.

A hybrid simulation integrating molecular dynamics and particle-in-cell methods for improved laser-target interaction

Ultra-thin targets (less than 10 nm), such as graphene, can be irradiated with relativistic intensity lasers to generate energetic ions. However, the laser prepulse can prematurely destroy these targets and significantly influence the final ion energies. Due to the limitations of the conventional hydrodynamic model, simulating the interaction between ultra-thin targets and a prepulse is infeasible. To overcome this issue, we propose a hybrid simulation technique in this study. This technique involves simulating the target-prepulse interaction using molecular dynamics (MD) simulation, which is then combined with the particle-in-cell simulation for the target-main pulse interaction, in order to accurately model the entire laser-target interaction dynamics. A realistic, experimentally measured laser intensity profile for the prepulse is used for the MD simulation, and the particle energies from this hybrid simulation are found to be in good agreement with the experiment.

Enhancing aqueous zinc-ion energy storage performance with ion-mediating carbon quantum dots-modified separators regulating zinc deposition behavior

Aqueous zinc-ion batteries (AZIBs) hold promising applications owing to their safety, cost-effectiveness, and competitive capacity. However, issues such as zinc dendritic formation and side reactions severely impede their practical viability. Utilizing carbon quantum dots (CQDs) to modify cheap, tenacious, and highly hydrophilic filter paper (FP) as separator effectively improves the electrochemical performance of zinc ion energy storage systems. The structured arrangement of CQDs redistributes zinc ion transport and induces uniform zinc icon deposition, thereby improving zinc ion reaction kinetics. Moreover, the rich functional groups on the surface of CQDs readily form hydrogen bonds with active H2O, further inhibiting corrosion reactions. With the assistance of CQDs, the FP-CQDs separator maintains high ionic conductivity and a high zinc-ion transference number, ensuring dendrite-free and corrosion-resistant operation with high coulombic efficiency and a prolonged lifespan of 1200 h at 1 mA cm−2. Zn//AC hybrid capacitors incorporating FP-CQDs separator demonstrate superior capacity retention compared to those using FP separator alone, with a high capacity retention after 600 cycles at 1 A/g, while Zn//V2O5 full batteries also exhibit excellent cycling stability. Given these findings, this study presents a new composite separator for advanced aqueous zinc-ion energy storage systems.

Effects of surface anisotropy on the surface morphological response of plasma-facing tungsten

Surface free energy has been hypothesized as the cause behind the experimental evidence (Parish et al., 2014) of a strong correlation between crystallographic orientation and surface morphology changes in helium ion-irradiated tungsten at the early stages of ‘fuzz’ growth in fusion plasma-facing tungsten. Here, this hypothesis is tested through self-consistent dynamical simulation based on an atomistically informed model of surface evolution in plasma-irradiated tungsten. Low-energy helium plasma irradiation of a tungsten surface, even when the ion energy is below the sputtering threshold, generates surface vacancy-adatom pairs in addition to adatoms from the flux of self-interstitial atoms to the surface resulting from the growth of high-pressure helium bubbles. Along with the stress-driven surface morphological instability as the primary driving force, preferential diffusion of these surface adatoms modulated by the associated Ehrlich–Schwoebel (ES) barriers, combined with the surface free energy anisotropy drive the anisotropic surface nanostructure growth. Simulation results for helium irradiation on W(100) show growth of pyramidal surface features, akin to experimental observations. This work confirms the hypothesis on the effect of tungsten surface crystallographic orientation on helium-ion-induced surface morphology changes, where surface mound formation is the outcome of a stress-driven surface morphological instability, while the anisotropic growth of the mounds is controlled by the ES-barrier-modulated anisotropic surface adatom diffusion and faceting of the mounds is controlled by the surface free energy anisotropy.

Effects of growth rate and dynamic substrate tilt on properties of Au-Ta alloy films deposited by high-power impulse magnetron sputtering

Gold‑tantalum (AuTa) alloys are promising for next-generation hohlraums for magnetically-assisted indirect-drive inertial confinement fusion. Hohlraum fabrication involves sputter deposition of ultrathick coatings on sphero-cylindrical substrates. The control of physical properties of such coatings remains a challenge. Here, we systematically study effects of the growth rate and dynamic substrate tilt on properties of AuTa4 films deposited onto rotating planar substrates mounted at different tilt angles to mimic different regions of the sphero-cylindrical surface of a hohlraum. We use high-power impulse magnetron sputtering (HiPIMS) in the constant charge per pulse mode with a pulse duration of 100 μs, a charge per pulse of 190 μC, a peak target current of about 3 A, and the pulse frequency varied in the range of 400–1400 Hz. The Langmuir probe, mass-resolved ion energy spectrometry, and optical emission spectroscopy are used to monitor plasma discharge characteristics in order to isolate and study effects of the growth rate. The deposition rate and the ballistics and energetics of depositing species are estimated by Monte Carlo simulations. Results show that the film microstructure, crystallographic phase, residual stress, and electrical resistivity strongly depend on both the deposition rate and substrate tilt, highlighting their critical role in tailoring properties of AuTa films during hohlraum fabrication.

Transition from Surface to Volume Expansion in Argon Clusters Coulomb Explosion.

The intensity-difference spectrum technique is applied to record charge-state resolved ion energy spectra from the Coulomb explosion of small Ar clusters under well-resolved laser intensity conditions. The far-reaching control of the experimental parameters permits us to identify a striking change in the expansion pattern of the nanoplasma beyond a given intensity. The simultaneous characterization of ion charge state and energy uncovers that a reduction of the laser intensity leads to a development of low energy cuts in the ion yields, not present at higher fluence. The complex interplay of outer ionization, recombination, ion screening, and the phenomenon of ionization saturation favors a surface-driven expansion at low plasma electron temperatures. With increasing laser intensity a transition into a volume-driven Coulomb explosion is observed.

A Platform for Ultra-Fast Proton Probing of Matter in Extreme Conditions.

Recent developments in ultrashort and intense laser systems have enabled the generation of short and brilliant proton sources, which are valuable for studying plasmas under extreme conditions in high-energy-density physics. However, developing sensors for the energy selection, focusing, transport, and detection of these sources remains challenging. This work presents a novel and simple design for an isochronous magnetic selector capable of angular and energy selection of proton sources, significantly reducing temporal spread compared to the current state of the art. The isochronous selector separates the beam based on ion energy, making it a potential component in new energy spectrum sensors for ions. Analytical estimations and Monte Carlo simulations validate the proposed configuration. Due to its low temporal spread, this selector is also useful for studying extreme states of matter, such as proton stopping power in warm dense matter, where short plasma stagnation time (<100 ps) is a critical factor. The proposed selector can also be employed at higher proton energies, achieving final time spreads of a few picoseconds. This has important implications for sensing technologies in the study of coherent energy deposition in biology and medical physics.

Realization of Higher Resolution Charge Detection Mass Spectrometry.

Charge detection mass spectrometry (CD-MS) allows mass distributions to be measured for heterogeneous samples that cannot be analyzed by conventional MS. With CD-MS, the m/z and charge are measured for individual ions using a detection cylinder embedded in an electrostatic linear ion trap (ELIT). Imprecision in both the m/z and charge measurements contribute to the mass resolution. However, if the charge can be measured with a precision of <0.2 e the charge state can be assigned with a low error rate and the mass resolving power only depends on the m/z resolution. Prior to this work, the best resolving power demonstrated experimentally for CD-MS was 700. Here we demonstrate a resolving power of >14,600, 20-times higher than the previous best. Trajectory simulations were used to optimize the geometry and electrostatic potentials of the ELIT. We found conditions where the energy dependence of the oscillation frequency becomes parabolic, and then operated with a nominal ion energy at the minimum of the parabola. The 14,600 resolving power was obtained with a beam collimator before the ELIT. With the collimator removed, the resolving power of the optimized ELIT is 7300, which is still an order of magnitude higher than the previous best. The resolving power was demonstrated by resolving the isotope distributions for peptides and proteins. High resolution CD-MS measurements were then used to resolve the glycans on a monoclonal antibody and applied to the analysis of hepatitis B virus capsids. The results indicate that procedures for adduct removal need to be improved for the full benefit of the higher resolving power to be realized for higher mass species. However, these results represent a key step toward using CD-MS to analyze very complex protein mixtures where charge states are not well resolved in the m/z spectrum because of congestion from numerous overlapping peaks.

Deeper-band electron contributions to stopping power of silicon for low-energy ions.

This study provides accurate results for the electronic stopping cross sections of H, He, N, and Ne in silicon in low to intermediate energy ranges using various non-perturbative theoretical methods, including real-time time-dependent density functional theory, transport cross section, and induced-density approach. Recent experimental findings [Ntemou et al., Phys. Rev. B 107, 155145 (2023)] revealed discrepancies between the estimates of density functional theory and the observed values. We show that these discrepancies vanish by considering the nonuniform electron density of the deeper silicon bands for ion velocities approaching zero (v → 0). This indicates that mechanisms such as "elevator" and "promotion," which can dynamically excite deeper-band electrons, are active, enabling a localized free-electron gas to emulate ion energy loss, as pointed out by Lim et al. [Phys. Rev. Lett. 116, 043201 (2016)]. The observation and the description of a velocity-proportionality breakdown in electronic stopping cross sections at very low velocities are considered to be a signature of the contributions of deeper-band electrons.

Modulating the zinc ion flux and electric field intensity by multifunctional metal-organic complex interface layer for highly stable Zn anode

The uncontrollable growth of Zn dendrites accompanied by side reactions severely impedes the industrialized process of zinc ion electrochemical energy storage devices. Herein, we propose a practical metal-organic complex interface layer to manipulate the zinc ion flux and electric field intensity, enabling highly homogeneous zinc electrodeposition. The zinc-terephthalic acid complex (ZnPTA) with lower adsorption energy for zinc ion (−1.3 eV) builds a zincophilic interface favoring the ordered nucleation and growth of Zn. Moreover, the ZnPTA layer can serve as physical barrier to protect the newly deposited Zn from corrosion in the aqueous electrolyte. The modified Zn anode with the ZnPTA layer (ZnPTA@Zn) demonstrates excellent cycling stability more than 3000 h at 1 mA/cm2. Besides, the zinc-ion battery and zinc-ion hybrid capacitor using the ZnPTA@Zn electrode deliver outstanding cycle performance (up to 5500 cycles with high residual capacity ratio of 77.9%). This work provides a promising metal-organic complex interface design on enhancing the performance of Zn metal anode.