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The effect of ion pairing on speciation and transport in ion exchange membranes at varying hydration levels: A four-state model

Understanding ion pairing in ion exchange membranes (IEMs) is essential for advancing IEM applications in energy and environmental technologies. Here, this study introduces a four-state molecular dynamics model to quantify speciation and transport within Nafion-117, specifically examining the role of ion pairing in monovalent and divalent counterions (NaCl, Na 2 SO 4 , and MgSO 4 ). By analyzing radial distribution functions (RDFs) and molecular snapshots, we distinguish ion pairing modes and classify counterions into four states: condensed counterion, condensed ion pair, free ion pair, and free counterion. A key finding is that while divalent counterions (e. g., Mg 2+ ) maintain stable speciation across hydration levels, monovalent counterions (e.g., Na + ) show notable speciation shifts with hydration. Both monovalent and divalent counterions are not diffusive when condensed onto the polymer (sorbed to membrane functional groups). In contrast, free counterions are diffusive across all hydration levels. To evaluate the overall diffusivity of counterions, four-state fractions and diffusivities are computed, each contributing to counterion transport. The condensed/free ion speciation for multivalent sulfate salts aligns with previous revisions to the Donnan-Manning framework that include ion pairing, thereby validating its relevance to established membrane theories. The four-state model's diffusivity results support several current ion exchange assumptions, including that the condensed counterions are immobile, while uncondensed counterions are mobile. The four-state model offers insights into contact ion pairing within IEMs, highlighting its potential even when undetected in aqueous solution experiments. This work advances the theoretical understanding of counterion speciation in IEMs while identifying model limitations that suggest avenues for refinement, such as distinguishing water-mediated ion pairs between fully hydrated ions.

Ion exchange membranes

Ion-Molecule Reactions and Ion Kinetics in DC Townsend Discharges in Dielectric Gases

In gas discharges the identify, transport, relative intensities, and kinetic energy distributions (KEDs) of ions may be dominated by ion-molecule reactions. In order to understand these discharges, there is a need for cross section data for various ion-molecule reactions, including symmetric and asymmetric charge-transfer, collisional detachment, and ion conversion reactions, especially for low to intermediate ion-impact energies. In view of the importance of dielectric gases, we have recently measured the KEDs of various positive and negative ions produced in DC Townsend discharges in SF6, CF4, CHF3, O2, and CO2. The relative abundance and mean energies of ions are obtained from the measured KEDs. The effective cross sections (Qeff) describing the KEDs of various ions can be derived by using the mean ion energies and the electric field-to-gas density ratios (E/N). In the case of SF6 and O2 discharges, the determined cross sections (Qeff) for the negative-ion molecule reactions are consistent with previously measured cross section data obtained by crossed-beam experiment. The availability of these cross section values enabled us to understand the ion data reasonably well. However, the lack of adequate cross section data for positive ions in all of the above gases is a major obstacle in understanding ion transport in these gas discharges.

Rao, M. V. V. S.

Are Ring Current Ions Lost in Electromagnetic Ion Cyclotron Wave Dispersion Relation?

Electromagnetic ion cyclotron (EMIC) waves are widely observed in the inner and outer magnetosphere, at geostationary orbit, at high latitudes along the plasmapause, and at the ionospheric altitudes. Interaction of the Ring Current (RC) ions and EMIC waves causes ion scattering into the loss cone and leads to decay of the RC, especially during the main phase of storms when the RC decay times of about one hour or less are observed. The oblique EMIC waves damp due to Landau resonance with the thermal plasmaspheric electrons, and subsequent transport of the dissipating wave energy into the ionosphere below causes an ionosphere temperature enhancement. Induced scattering of these waves by the plasmaspheric thermal ions leads to ion temperature enhancement, and forms a so-called hot zone near the plasmapause where the temperature of core plasma ions can reach tens of thousands of degrees. Relativistic electrons in the outer radiation belt also interact well with the EMIC waves, and during the main and/or recovery phases of the storms these electrons can easily be scattered into the loss cone over a time scale from several hours to a day. The plasma density distribution in the magnetosphere and the ion content play a critical role in EMIC wave generation and propagation, but the wave dispersion relation in the known RC-EMIC wave interaction models is assumed to be determined by the thermal plasma distribution only. In these models, the modification of the EMIC wave dispersion relation caused by the RC ions is not taken into account, and the RC ions are only treated as a source of free energy in order to generate EMIC waves. At the same time, the RC ions can dominate the thermal magnetospheric content in the night MLT sector at great L shells during the main and/or recovery storm phase. In this study, using our self-consistent RC-EMIC wave model [Khazanov et al., 2006], we simulate the May 1998 storm in order to quantify the global EMIC wave redistribution caused by taking into account the RC ions in the EMIC wave dispersion relation. The dramatic wave pattern redistribution is observed in the postdusk-predawn MLT sector (night sector) for L greater than 5. We found the intense EMIC waves (about a few nT) there during the main and early recovery phases of the storm. The observed wave generation in this sector is caused by taking into account the EMIC wave dispersion change due to the RC ions. There are no waves at these locations in our model if the RC ions are taken into account in the wave growth rate only, and the wave dispersion relation is only governed by the thermal plasmaspheric model.

Khazanov, G. V.

Effect of Ring Current Ions on Electromagnetic Ion Cyclotron Wave Dispersion Relation

Electromagnetic ion cyclotron (EMIC) waves are widely observed in the inner and outer magnetosphere, at geostationary orbit, at high latitudes along the plasmapause, and at the ionospheric altitudes. Interaction of the Ring Current (RC) ions and EMIC waves causes ion scattering into the loss cone and leads to decay of the RC, especially during the main phase of storms when the RC decay times of about one hour or less are observed. The oblique EMIC waves damp due to Landau resonance with the thermal plasmaspheric electrons, and subsequent transport of the dissipating wave energy into the ionosphere below causes an ionosphere temperature enhancement. Induced scattering of these waves by the plasmaspheric thermal ions leads to ion temperature enhancement, and forms a so-called hot zone near the plasmapause where the temperature of core plasma ions can reach tens of thousands of degrees. Relativistic electrons in the outer radiation belt also interact well with the EMIC waves, and during the main and/or recovery phases of the storms these electrons can easily be scattered into the loss cone over a time scale from several hours to a day. The plasma density distribution in the magnetosphere and the ion content play a critical role in EMIC wave generation and propagation, but the wave dispersion relation in the known RC-EMIC wave interaction models is assumed to be determined by the thermal plasma distribution only. In these models, the modification of the EMIC wave dispersion relation caused by the RC ions is not taken into account, and the RC ions are only treated as a source of free energy in order to generate EMIC waves. At the same time, the RC ions can dominate the thermal magnetospheric content in the night MLT sector at great L shells during the main and/or recovery storm phase. In this study, using our self-consistent RC-EMIC wave model [Khazanov et al., 2006], we simulate the May 1998 storm in order to quantify the global EMIC wave redistribution caused by taking into account the RC ions in the EMIC wave dispersion relation. The dramatic wave pattern redistribution is observed in the postdusk-predawn MLT sector (night sector) for L greater than 5. We found the intense EMIC waves (about a few nT) there during the main and early recovery phases of the storm. The observed wave generation in this sector is caused by taking into account the EMIC wave dispersion change due to the RC ions. There are no waves at these locations in our model if the RC ions are taken into account in the wave growth rate only, and the wave dispersion relation is only governed by the thermal plasmaspheric model.

Gamayunov, K. V.

Beyond Ion Migration in Metal Halide Perovskites: Toward a Broader Photoelectrochemistry Perspective

Ion migration is a broad term used to account for the degradation of halide perovskite materials and devices. However, ion mobility is only one piece of the full picture-mobile ions/defects are first created, then transported, and eventually annihilated or immobilized. In this Perspective, we summarize emerging work that shows how tractable photochemical and Faradaic reactions provide a continuous source of ions to migrate. Furthermore, we discuss strategies to fundamentally manipulate ion migration by targeting specific electrochemical and reduction/oxidation mechanisms. This highlights the important role of defect photoelectrochemistry, as well as the soft nature of the perovskite lattice, in ion migration and self-healing. We conclude that distinguishing more detailed processes involved in “ion migration”, with an emerging focus on the reactions that form mobile ionic defects, is necessary to greatly improve the stability of devices and open up more technological applications.

defects

On the role of ion temperature gradient turbulence in driving ion thermal transport in neutral beam injection-heated L-mode plasmas in a superconducting tokamak

In this paper, we report a detailed experimental study of the role of ion-temperature-gradient driven turbulence in driving ion thermal transport in neutral beam injection (NBI)-heated L-mode plasmas in Experimental Advanced Superconducting Tokamak (EAST) (Wan et al 2000 Nucl. Fusion 40 1057) coupled with linear and nonlinear gyrokinetic simulations. Significant ion-scale turbulence k ⟂ < cm −1 (k ⟂ < 1.5, where k ⟂ where is the perpendicular wavenumber and ρ s is the ion gyroradius calculated using local electron temperature T e ), measured with a microwave reflectometer, is observed in the plasma core at for r/a ≈ 0.265 and 0.5 (where r is half the diameter of the closed flux surface at a given radial position, and a is half the diameter of the last closed flux surface). Local linear stability analysis with experimental equilibrium quantities at these two radial locations using the GS2 gyrokinetic code shows that the most unstable ion-scale micro-instability is the ion temperature gradient (ITG) mode. Since the computed maximum ion-scale linear growth rates are larger than the local Waltz-Miller E × B shearing rate (Waltz and Miller 1999 Phys. Plasmas 6 4265), the E × B shear is unable to suppress ion-scale turbulence, consistent with the experimental observation of ion-scale turbulence. Experimental ion and electron thermal transports, calculated with power balance analysis, are both anomalous with ion thermal transport being the dominant channel. Nonlinear gyrokinetic simulations using the electrostatic global particle-in-cell gyrokinetic tokamak simulation (GTS) code (Weixing Wang et al 2010 Phys. Plasmas 17 072511) show good quantitative agreement between predicted ion thermal transport and that from the power balance analysis. These results demonstrate for the first time the important role of ITG turbulence in driving thermal transport in NBI-heated L-mode plasmas in EAST, showing the effectiveness of GTS code in simulating electrostatic turbulence in EAST and the need of suppressing ITG turbulence to improve energy confinement in EAST.

Sun, P. J. [Chinese Academy of Sciences (CAS), Hef

Alfven ion-cyclotron heating of ionospheric O(+) ions

Transversely heated ionospheric ions, in particular O(+) ions, are often observed flowing upward along auroral field lines. Currents observed in association with the transversely heated ions can drive shear Alfven waves and electrostatic ion-cyclotron waves unstable which can, in turn, be resonantly absorbed by the ions to produce the heating. Particle simulations are used to examine self-consistently the excitation of these waves and the associated heating. It is shown that the growth of the electrostatic ion-cyclotron waves quickly becomes suppressed as the ions become heated and the dominant wave fields are those of the shear Alfven wave. The resultant transverse ion heating is larger and faster than that produced by solely electrostatic ion-cyclotron wave heating. Due to trapping of ions by the shear Alfven wave, the temperature of the O(+) ions remains comparable to that of the H(+) ions.

Winglee, R. M.

Versatile system for ion energy measurements generated by pulsed laser ionization: Insights into electron-ion dynamics

Ion energy distributions generated by pulsed laser interactions with materials are essential for applications ranging from materials science to oncology. Ion energy characterization is particularly important for an emerging mass spectrometry technique called virtual-slit cycloidal mass spectrometry (VS-CMS). The ion energy distribution influences the design and performance of VS-CMS instruments, as well as the efficacy of laser-driven ionization methods in various fields. Several established techniques, including the retarding potential method, time-of-flight (TOF) analysis, and electrostatic energy analyzers, have been employed to measure ion energy distributions. The wide range of ion energies reported highlights the strong dependence of ion energy on laser parameters, target materials, and experimental conditions, as well as the necessity of making independent measurements of the ion energy distribution for specific laser systems and materials. This paper presents the design and characterization of a simple TOF-based apparatus for measuring ion energy distributions from pulsed laser ionization without external fields. This approach minimizes perturbation of electron-ion dynamics and enables simultaneous energy measurements at multiple spatial positions. Here, the apparatus was tested using a nanosecond pulsed Nd:YAG laser operating at 1064 nm, 532 nm, and 266 nm on solid copper sheets at various laser fluences. Simultaneous measurements at different distances provide new insights into ion-electron interactions post-ionization and demonstrate the influence of laser wavelength and fluence on ion energy distributions.

Ion energy

Ion Size Effects on the Thermodynamic, Kinetic, and Mechanical Properties during Ion Exchange in Solid-State Electrolytes

Ion exchange offers a pathway to impose residual compressive stresses to mitigate the electro-chemo-mechanical cracking of solid-state electrolytes such as lithium lanthanum zirconium oxide. This study uses a coupled multiscale framework (integrating density functional theory (DFT), molecular dynamics (MD), and continuum modeling) to examine how exchange ion size influences stress, diffusion, fracture toughness, and electronic properties. Larger isovalent ions (Na + , Ag + , K + ) were exchanged with Li + , with DFT confirming their preference for octahedral 96h sites and a linear relationship between ion size and chemical free expansion coefficient. MD simulations reveal stress and concentration effects on exchange ion diffusivity at elevated temperatures, with Na + and Ag + maintaining favorable mobility while K + showing concentration-dependent clustering. Continuum modeling predicts the range of fracture strength improvements and the required ion exchange concentration profile. It was shown that a 5% surface exchange concentration can induce ∼0.6 GPa of surface compressive stress using Na + and ∼1.0 GPa of surface compressive stress using Ag + . On the other hand, larger ion exchange species may penalize Li + diffusivity by increasing the activation volume and activation energy. Interestingly, Na + has a negligible penalty on Li-ion diffusivity. The room temperature Li + ion diffusivity is reduced by ∼40% with Ag + ion exchange. Electronic band structure analysis shows no size-dependent change in the bandgap, though Ag + introduces localized defect states near the valence band maximum. This study highlights ion size as a key factor in optimizing LLZO properties, offering a framework to improve the solid-state battery performance.

Jagad, Harsh D. [Brown Univ., Providence, RI (Unit

Specific ion effects on ion transport in charged polymer membranes

Selective separation of like-charged ions is a central challenge in applications such as critical mineral recovery. Electrochemical membrane–based separations offer promising pathways to address this need, but a limited fundamental understanding of ion transport in charged polymer membranes hampers the development of highly selective materials. This study elucidates the role of specific ion effects (SIEs) in ion transport through charged polymer membranes by integrating experimental measurements of ion mobility and in situ ion/ion and ion/water interactions in model charged polymer membranes with results from molecular dynamics simulations on analogous systems. We demonstrate that solvent-mediated ion interactions drive pronounced SIEs within the studied membranes, with the ion softness, i.e., the malleability of ion hydration shells, from hard/soft acid/base (HSAB) theory emerging as a key predictor of transport properties. HSAB theory also explains the observed mechanism of solvent-mediated ion interactions. Our findings offer a mechanistic framework for designing membranes with tailored ion selectivity, potentially enabling efficient separations of chemically similar ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Thermal Electron Contributions to Current-Driven Instabilities: SCIFER Observations in the 1400-km Cleft Ion Fountain and Their Implications to Thermal Ion Energization

SCIFER TECHS observations of the variations in the thermal electron distribution in the 1400-km altitude cleft are associated with periods of intense ion heating and field-aligned currents. Energization of the thermal ion plasma in the mid-altitude cleft occurs within density cavities accompanied by enhanced thermal electron temperatures, large field-aligned thermal electron plasma flows and broadband low-frequency electric fields. Variations in the thermal electron contribution to field-aligned current densities indicate small scale (approximately 100's m) filamentary structure embedded within the ion energization periods. TECHS observations of the field-aligned drift velocities and temperatures of the thermal electron distribution are presented to evaluate the critical velocity thresholds necessary for the generation of electrostatic ion cyclotron and ion acoustic instabilities. This analysis suggests that, during periods of thermal ion energization, sufficient drift exists in the thermal electron distribution to excite the electrostatic ion cyclotron instability. In addition, brief periods exist within the same interval where the drift of the thermal electron distribution is sufficient to marginally excite the ion acoustic instability. In addition, the presence an enhancement in Langmuir emission at the plasma frequency at the center of the ion energization region, accompanied by the emission's second-harmonic, and collocated with observations of high-frequency electric field solitary structures suggest the presence of electron beam driven decay of Langmuir waves to ion acoustic modes as an additional free energy source for ion energization.

Adrian, Mark L.

Monte Carlo simulation analysis for radiation damage on Glidcop Al-15 caused by 17-20 MeV/u heavy ions

The Facility for Rare Isotope Beams (FRIB) SRF linear heavy-ion accelerator is designed to accelerate all ions up to uranium to a maximum beam power of 400 kW. Several beam intercepting devices (BIDs) are essential to the successful operation of the accelerator, including a low power charge selector (LPCS) made of copper containing 0.15% precipitated aluminum oxide by weight called Glidcop Al-15. As FRIB ramps up the primary beam power beyond the current 20 kW level, the charge selector must withstand higher radiation damage rates, typically measured in displacements per atom (dpa). Significant beam induced radiation damage including significant deformation, like swelling, blistering, and cracking has been observed on a recently removed LPCS. We also observed physical features up to about 5.5 mm wide and appear to be deeper than the projected range of any ions. This paper presents the results of Monte Carlo simulations carried out using the Particle and Heavy Ion Transport code System (PHITS), quantifying the total damage dose and ion concentration, etc. Simulating an accurate irradiation history is essential to determining the scope of post irradiation examination (PIE) work.

Fletcher, Ethan [Michigan State U.]

Critically assessing sodium-ion technology roadmaps and scenarios for techno-economic competitiveness against lithium-ion batteries

Sodium-ion batteries have garnered notable attention as a potentially low-cost alternative to lithium-ion batteries, which have experienced supply shortages and price volatility for key minerals. Here we assess their techno-economic competitiveness against incumbent lithium-ion batteries using a modelling framework incorporating componential learning curves constrained by minerals prices and engineering design floors. We compare projected sodium-ion and lithium-ion price trends across over 6,000 scenarios while varying Na-ion technology development roadmaps, supply chain scenarios, market penetration and learning rates. Assuming that substantial progress can be made along technology roadmaps via targeted research and development, we identify several sodium-ion pathways that might reach cost-competitiveness with low-cost lithium-ion variants in the 2030s. In addition, we show that timelines are highly sensitive to movements in critical minerals supply chains—namely that of lithium, graphite and nickel. Our modelled outcomes suggest that being price advantageous against low-cost lithium-ion variants in the near term is challenging and increasing sodium-ion energy densities to decrease materials intensity is among the most impactful ways to improve competitiveness.

25 ENERGY STORAGE

Development Efforts Expanded in Ion Propulsion: Ion Thrusters Developed With Higher Power Levels

The NASA Glenn Research Center was the major contributor of 2-kW-class ion thruster technology to the Deep Space 1 mission, which was successfully completed in early 2002. Recently, NASA s Office of Space Science awarded approximately $21 million to Glenn to develop higher power xenon ion propulsion systems for large flagship missions such as outer planet explorers and sample return missions. The project, referred to as NASA's Evolutionary Xenon Thruster (NEXT), is a logical follow-on to the ion propulsion system demonstrated on Deep Space 1. The propulsion system power level for NEXT is expected to be as high as 25 kW, incorporating multiple ion thrusters, each capable of being throttled over a 1- to 6-kW power range. To date, engineering model thrusters have been developed, and performance and plume diagnostics are now being documented. The project team-Glenn, the Jet Propulsion Laboratory, General Dynamics, Boeing Electron Dynamic Devices, the Applied Physics Laboratory, the University of Michigan, and Colorado State University-is in the process of developing hardware for a ground demonstration of the NEXT propulsion system, which comprises a xenon feed system, controllers, multiple thrusters, and power processors. The development program also will include life assessments by tests and analyses, single-string tests of ion thrusters and power systems, and finally, multistring thruster system tests in calendar year 2005. In addition, NASA's Office of Space Science selected Glenn to lead the development of a 25-kW xenon thruster to enable NASA to conduct future missions to the outer planets of Jupiter and beyond, under the High Power Electric Propulsion (HiPEP) program. The development of a 100-kW-class ion propulsion system and power conversion systems are critical components to enable future nuclear-electric propulsion systems. In fiscal year 2003, a team composed of Glenn, the Boeing Company, General Dynamics, the Applied Physics Laboratory, the Naval Research Laboratory, the University of Wisconsin, the University of Michigan, and Colorado State University will perform a 6-month study that will result in the design of a 25-kW ion thruster, a propellant feed system, and a power processing architecture. The following 2 years will involve hardware development, wear tests, single-string tests of the thruster-power circuits and the xenon feed system, and subsystem service life analyses. The 2-kW-class ion propulsion technology developed for the Deep Space 1 mission will be used for NASA's discovery mission Dawn, which involves maneuvering a spacecraft to survey the asteroids Ceres and Vesta. The 6-kW-class ion thruster subsystem technology under NEXT is scheduled to be flight ready by calendar year 2006. The less mature 25- kW ion thruster system under HiPEP is expected to be ready for a flight advanced development program in calendar year 2006.

Patterson, Michael J.

Impulsively Reflected Ions: A Plausible Mechanism for Ion Acoustic Wave Growth in Collisionless Shocks

We present recent high time resolution observations from an oblique (43 deg) shock crossing from the Magnetospheric Multiscale mission. Short-duration bursts between 10 and 100 ms of ion acoustic waves are observed in this event alongside a persistent reflected ion population. High time resolution (150 ms) particle measurements show strongly varying ion distributions between successive measurements, implying that they are bursty and impulsive by nature. Such signatures are consistent with ion bursts that are impulsively reflected at various points within the shock. We find that, after instability analysis using a Fried-Conte dispersion solver, the insertion of dispersive ion bursts into an already stable ion distribution can lead to wave growth in the ion acoustic mode for short durations of time. We find that impulsively reflected ions are a plausible mechanism for ion acoustic wave growth in the terrestrial bow shock and, furthermore, suggest that wave growth can lead to a small but measurable momentum exchange between the solar wind ions and the reflected population.

Goodrich, Katherine A.

Analysis of fast-ion losses measured in MAST-U via infrared thermography and a Fast Ion Loss Detector

Fast-ion losses need to be monitored to avoid damage to plasma facing components. In existing experimental devices, the scintillator-based fast-ion loss detector (FILD) is the most advanced diagnostic for measuring fast-ion losses. However, FILDs provide only local information about the losses. Infrared (IR) thermography can be used as a complementary tool for more global monitoring of the deposition of fast-ion losses on the wall, at the expense of no velocity-space resolution. IR cameras measure the temperature of the plasma facing components. This measurement, determined by a combined effect of the thermal plasma, radiation, neutrons and fast-ion losses, can be decomposed to infer the fast-ion load on the tokamak wall. In this manuscript, a workflow to estimate fast-ion losses via IR thermography is applied to the MAST-U spherical tokamak, using a 1D approximation to extract the experimental heat flux on the FILD front face from IR data. To numerically estimate the different contributions to this total heat flux, the field-line tracing environment SMITER is used to calculate the thermal plasma contribution, the orbit-following Monte-Carlo code ASCOT to estimate the fast-ion losses, and bolometry measurements for the radiation. To validate the workflow, two discharges, L-mode plasmas with low MHD activity, were executed using on and off-axis beams, respectively. The experimentally and numerically estimated heat flux are of the same order of magnitude for the on-axis heated scenario, with a strong dependence of the estimated fast-ion losses contribution on the fit to the kinetic profiles used as input. This is also true for the off-axis heated scenario, where the total numerically estimated heat flux is 2.1 or 1.3 times higher than the maximum experimentally estimated heat flux, depending on the ASCOT input used.

FILD

Direct Observations of Ion Densities at Functionalized Interfaces to Test Hypotheses Regarding the Origin of Specific Ion Effects

Interactions of anions with protonatable groups were investigated using X-ray fluorescence near total reflection (XFNTR) on floating monolayers at the surface of water. The number of ions attracted to the interfacial region, which XFNTR measures directly, is ion-specific as well as monolayer-specific. Our observation of the distinctly different behaviors of ClO 4 – and ReO 4 – , two ions with the same tetrahedral structure and almost the same sizes and hydration enthalpies, challenges current theories of ion specificity. Our observations are inconsistent with not only the Gouy–Chapman model (as expected) but also size-modified Poisson–Boltzmann theory and the “law of matching water affinity”. Furthermore, we suggest that factors other than ion size and ion–water interactions, including possibly ion–ion interactions and lateral ordering at the interface, must be considered to account for specific ion effects.

36 MATERIALS SCIENCE

Elucidating the Link Between Alkali Metal Ions and Reaction-Transport Mechanisms in Cathode Electrodes for Alkali-ion Batteries

Our long-term goal is to improve the reliability of electrode materials and their ability to transport and store various metal ions for electrochemical energy storage applications. The main objective of this work was to investigate the intrinsic relationship between the role of alkali metal ions and electrochemically driven mechanical stability and kinetic properties of battery materials. The overall question was “What is the role of alkali metal ions on the electrochemical and mechanical behavior of cathode electrodes? Our guiding hypothesis was that intercalation of larger alkali metal ions (Na and K) inevitably alters the coupled transport-reaction processes during battery operation in organic electrolytes, leading to more intensive chemo-mechanical instabilities in cathode electrodes, resulting in rapid capacity fade. To validate the hypothesis, we experimentally characterized the reaction-transport processes and governing forces driving the instability of electrode materials in different alkali metal-ion environments. The project had three main tasks. The first one was to investigate intercalation-induced strains and associated stress generation, and their impact on structural deformations in composite cathode electrodes. The second task focused on identifying potential-dependent dynamic changes in the electrode-electrolyte interface in alkali metal ion batteries. The last task was focused on determining how larger alkali metal ions with slower diffusivity affect the transport-mechanics coupling at faster scan rates, compared to smaller ions with faster diffusivity in electrodes. We shortly provided the outcome of each task in the accomplishment section. This project produced 10 peer-reviewed publications (9 research papers and one review manuscript) and supported two Ph.D. students, who graduated from Oklahoma State University.

25 ENERGY STORAGE