High Charge States Research Articles

Oxygen Dimerization as a Defect-Driven Process in Bulk LiNiO2.

To explore the possibility of oxygen dimerization-particularly, the formation of molecular oxygen-like species-in the bulk of LiNiO2 lithium ion cathode materials at high states of charge, we conduct a redox-product structure search inspired by recent methodological developments for point-defect structure prediction. We find that (1) delithiated Li1-x NiO2 (x = 1) has good kinetic stability toward decomposition into molecular oxygen and reduced transition-metal oxides but (2) defects can act as nucleation sites for oxygen dimerization. These results help reconcile conflicting reports on the formation of bulk molecular oxygen in LiNiO2 and other nickel-rich cathode materials, highlighting the role of defect chemistry in driving the bulk degradation of these compounds.

A comparative study on state-of-charge estimation for lithium-rich manganese-based battery based on Bayesian filtering and machine learning methods

In this paper, a comparative study on the state of charge (SOC) estimation of the lithium-rich manganese-based battery (LRMB) has been conducted by systematically considering the equivalent circuit model (ECM), aging state and algorithms. The results show that the first-order RC model combined with the Extended Kalman filter (EKF) is more suitable for the SOC estimation of the LRMB when the battery decays less severely. The maximum value of root mean square error of SOC estimation error no exceeds 1.6 % under various dynamic operating conditions, which can well meet the practical application. Besides, the first-order model based EKF algorithm occupies least computing resource and simultaneously possesses the best convergence velocity against the initial SOC value deviation. When the LRMB suffers a severe aging, the SOC estimation performance decreases significantly with the max error exceeding 6 %, to overcome this, a new algorithm combined deep learning and Extend Kalman filter (EKF) is proposed, which exhibit high SOC estimation accuracy with the RMSE less than 0.16 %. In summary, a systematic study about the SOC estimation of LRMB has been carried out, which can provide great guidance for the future engineering application of LRMB.

Annealing Modulation Defect Chemistry toward High-Performance Sodium-Layered Cathodes.

Layered sodium transition-metal oxides generally encounter severe capacity decay and inferior rate performance during cycling, especially at a high state of charge. Herein, defect concentration is rationally modulated to explore the impact on electrochemical behavior in NaNi1/3Fe1/3Mn1/3O2 layered oxides. Bulk vacancies are increased through annealing in an oxygen-rich atmosphere, demonstrated by electron paramagnetic resonance measurement. It is found that the cathode with enriched oxygen vacancies exhibits significantly enhanced reversibility of redox reactions with a higher initial Coulombic efficiency of 90.0%. Furthermore, the reduced volume variations during the initial charge/discharge process are also confirmed by in situ X-ray diffraction. As a result, the oxygen-vacancy-rich cathode shows great cycling stability and superior rate performances. Also, full cells deliver a specific capacity of approximately 145.2 mAh g-1 at 0.5 C, with a high capacity retention of 78.3% after 100 cycles. This work presents a viable strategy for designing Na+ intercalated cathodes with a high-energy density.

Estimation of the Electric Field in Atom Probe Tomography Experiments Using Charge State Ratios.

Kingham [(1982). The post-ionization of field evaporated ions: A theoretical explanation of multiple charge states. Surf Sci116(2), 273-301] provided equations for the probability of observing higher charge states in atom probe tomography (APT) experiments. These "Kingham curves" have wide application in APT, but cannot be analytically transformed to provide the electric field in terms of the easily measured charge state ratio (CSR). Here we provide a numerical scheme for the calculation of Kingham curves and the variation in electric field with CSR. We find the variation in electric field with CSR is well described by a simple two- or three-parameter equation, and the model is accurate to most elements and charge states. The model is applied to experimental APT data of pure aluminium and a microalloyed steel, demonstrating that the methods described in this work can be easily applied to a variety of APT problems to understand electric field variations.

Depletion of Electrolyte Salt Upon Calendaric Aging of Lithium-Ion Batteries and its Effect on Cell Performance

The trend for increased nickel content in layered transition metal oxide cathode active materials and increasing charging cut-off voltages aggravates aging of lithium-ion battery cells at high state of charge (SOC). We investigate the calendaric aging behavior of large-format automotive prototype cells and laboratory single-layer pouch cells at high but realistic cell voltages/SOCs and demonstrate that electrolyte oxidation in combination with follow-up reactions can cause a significant loss of the LiPF6 salt in the electrolyte. For this, we analyze the LiPF6 concentration in aged cells, the generation of H2 upon storage, and the cell resistance for different aging conditions. We show that the LiPF6 loss is a critical aging phenomenon, as it cannot readily be detected by capacity fading measurements at low/medium C-rates or by cell resistance measurements, while it severely reduces rate and fast-charging capability. Under certain circumstances, LiPF6 loss can even lead to a temporary capacity increase due to conversion of the conducting salt in the electrolyte to cyclable lithium in the active material. Finally, we suggest a possible reaction mechanism and a simple accounting model to keep track of how different side reactions involved in LiPF6 loss change the cyclable lithium inventory of a lithium-ion cell.

Extending a Multiphysics Li-Ion Battery Model from Normal Operation to Short Circuit and Venting

Mitigation of Li-ion battery system fires consists of reliable fault detection and proactive, fast discharge control. Both require modeling of failure modes due to high temperatures and currents between normal operation and thermal runaway. In this work, we present a control-oriented, reduced-order, multiphysics model that captures the electrochemical, thermal, gas generation, mechanical expansion, and venting behavior of NMC pouch cells undergoing an external short circuit (ESC) from different initial state-of-charge (SOC). The model is parameterized through experiments by fitting the solid-electrolyte interphase (SEI) decomposition rate, the cell’s thermal parameters, and the particle solid-phase diffusion parameters to capture the first venting timing, peak temperature, and diffusion-limited electrical behavior at high currents. Using a single parameter set, the multiphysics model can capture behavior during an ESC to predict whether a cell will generate gas and vent, predict the vent timing within 10 seconds of it occurring in the experiment, and maximum cell expansion pressure within 10 kPa for cells that did not vent. The model can also predict the SOC trajectory for cells with a high initial SOC within 6% SOC for the 15-minute discharge or until the cell vents.

Unlocking highly reversible V5+/V4+ redox reaction and fast-stable Na storage in NASICON cathodes by electronic structure optimization and solid-solution behavior regulation

It is formidable to fully exert NASICON-structured Na3V2(PO4)3's (NVP) energy density due to the serious structural degradation aroused from the undesirable phase evolution and transition metal ion migration upon high potential versus Na+/Na. To break through the energy limitation of NVP, we meticulously selected three classes of metal elements to employ a novel quaternary substitution in NVP. Theoretical calculation expresses that their 3p, 3d, 4 f orbits hybrid synergy can favor the electron rearrangement signally, increasing the accessibility of the V5+/V4+ redox reaction. Therefore, Na3V1.6(CrAlFeCe)0.1(PO4)3 (NVMP) cathode delivers a groundbreaking energy density of 420 Wh kg−1. Besides, the solid-solution mechanism of Na storage during the V5+/V4+ reaction process was validated by ex situ XRD, demonstrating the significant effect of quaternary substitution on inhibiting irreversible phase evolution under high charge states. Hence, NVMP can maintain the activated V5+/V4+ after 10000 cycles. The fast Na-storing kinetics of NVMP were analyzed by in situ EIS, in situ DRT, GITT, and various scan rate CV. This work provides new insights for adjusting electronic structure and Na storing behavior in NASICON cathodes.

Manipulating Local Chemistry and Coherent Structures for High-Rate and Long-Life Sodium-Ion Battery Cathodes.

Layered sodium transition-metal (TM) oxides generally suffer from severe capacity decay and poor rate performance during cycling, especially at a high state of charge (SoC). Herein, an insight into failure mechanisms within high-voltage layered cathodes is unveiled, while a two-in-one tactic of charge localization and coherent structures is devised to improve structural integrity and Na+ transport kinetics, elucidated by density functional theory calculations. Elevated Jahn-Teller [Mn3+O6] concentration on the particle surface during sodiation, coupled with intense interlayer repulsion and adverse oxygen instability, leads to irreversible damage to the near-surface structure, as demonstrated by X-ray absorption spectroscopy and in situ characterization techniques. It is further validated that the structural skeleton is substantially strengthened through the electronic structure modulation surrounding oxygen. Furthermore, optimized Na+ diffusion is effectively attainable via regulating intergrown structures, successfully achieved by the Zn2+ inducer. Greatly, good redox reversibility with an initial Coulombic efficiency of 92.6%, impressive rate capability (86.5 mAh g-1 with 70.4% retention at 10C), and enhanced cycling stability (71.6% retention after 300 cycles at 5C) are exhibited in the P2/O3 biphasic cathode. It is believed that a profound comprehension of layered oxides will herald fresh perspectives to develop high-voltage cathode materials for sodium-ion batteries.

Probing the Stability of a β-Hairpin Scaffold after Desolvation.

Probing the structural characteristics of biomolecular ions in the gas phase following native mass spectrometry (nMS) is of great interest, because noncovalent interactions, and thus native fold features, are believed to be largely retained upon desolvation. However, the conformation usually depends heavily on the charge state of the species investigated. In this study, we combine transition metal ion Förster resonance energy transfer (tmFRET) and ion mobility-mass spectrometry (IM-MS) with molecular dynamics (MD) simulations to interrogate the β-hairpin structure of GB1p in vacuo. Fluorescence lifetime values and collisional cross sections suggest an unfolding of the β-hairpin motif for higher charge states. MD simulations are consistent with experimental constraints, yet intriguingly provide an alternative structural interpretation: preservation of the β-hairpin is not only predicted for 2+ but also for 4+ charged species, which is unexpected given the substantial Coulomb repulsion for small secondary structure scaffolds.

Research and development activities to increase the performance of the CAPRICE ECRIS at GSI

At GSI the CAPRICE ECRIS is in operation to deliver high charge state ion beams from gaseous and metallic elements to the accelerator facility. A test campaign has been carried out at the ECR test bench to fulfill the demand for higher intensity and stability of high charge state ions and for mixed ion beams. The ion beam stability has been monitored by an Optical Emission Spectrometer (OES), which has been already used to check the plasma and the temperature of the resistively heated oven during metal ion beam operation, particularly for Ca ion beams. During the test campaign, it was investigated that the OES can be used for monitoring the stability of ion beams from gaseous elements and mixed ion beams, and the main achieved results are reported. The ion beams extracted from the ECRIS have been simulated with a particle tracking code in order to study and improve the beam matching into the RFQ. The preliminary results of the study together with possible modifications of the extraction column are presented.

Pulse-stretching out of the CANREB EBIS

The CANadian Rare isotope facility with Electron-Beam ion source (CANREB) at TRIUMF is set to deliver rare isotope beams in high charge states. In the Electron Beam Ion Source (EBIS) ions are charge-bred by collisions with an electron beam of up to 500 mA. A strong magnetic field (up to 6T) maximizes the overlap between ions and electron beam and increases the breeding efficiency. Ion confinement is maintained by a combination of an electrostatic field and the electron beam space-charge potential. Ions are released by lowering the trapping potential with a step function. The system is operated at a pulse repetition frequency up to 100 Hz. Due to the short trap length, this fast extraction scheme produces pulses shorter than 10 µs with high instantaneous rates that can saturate detectors in experiments. Stretching the pulse can be done using a slowly varying voltage function to modify trap electrode potentials instead of a step function. The ideal function produces a pulse with a flat top distribution and can be calculated by knowing the ion energy distribution inside the trap. The latest pulse-stretching results will be discussed including the latest pulse duration up to 1.4 ms that have been produced. The slow extraction scheme has also been used for a measurement of the effective energy distribution of the ions inside the trap.

Gas mixing and double frequency operation of the permanent magnet quadrupole minimum-B electron cyclotron resonance ion source CUBE-ECRIS

CUBE-ECRIS is a recently commissioned permanent magnet electron cyclotron resonance (ECR) ion source developed at the university of Jyväskylä accelerator laboratory. The special features of the new ion source design include an unconventional quadrupole minimum-B magnetic field structure and a slit beam extraction system necessitated by the line-shaped plasma loss fluxes. Gas mixing and double frequency operation are widely used methods to optimize high charge state ion production of conventional ECR ion sources. The work presented here demonstrates the applicability of these methods for boosting the high charge state beam currents of argon, krypton and xenon extracted from CUBE-ECRIS. Oxygen and helium were used as mixing gases and microwave frequencies between 10 and 11 GHz were used for single and double frequency operation. Gas mixing has a strong impact on the high charge state beam currents. For example, the highest observed charge state increased from 15+ to 19+ for krypton and from 16+ to 23+ for xenon with oxygen gas mixing. Double frequency operation provides an additional performance improvement, for example the currents of argon 9+ and 11+ beams, produced with gas mixing, increased 30% and 100% in double frequency operation at the same total power.

New Technique of Injecting Radioactive Ions into Charge Breeding ECR Ion Source

Cyclotron Institute at Texas A&M University started a project to develop the reacceleration of radioactive ions using the two operational cyclotrons and a Charge Breeding ECR ion source. The radioactive ions are produced primarily via (p,n) reactions using the IGISOL technique. The reaction products are transported into a Charge Breeder ECR ion source where their charge state is boosted from 1+ to higher charge states. The transport of the radioactive products and the injection into the ion source are very important for the efficiency of charge breeding. Two techniques have been used: acceleration–deceleration method (classic) and low - energy RF-only sextupole ion guide transport and injection method (innovative technique). The last method appears to be very efficient and great charge breeding efficiency was observed. The presentation of the entire project, the new injection technique, experimental results, and future plans will be discussed.

Novel modelling of metal atoms diffusion and ion transport in ECR plasma relevant to ion sources and in-plasma nuclear physics studies

Metals can be injected into electron cyclotron resonance ion sources (ECRIS) via different techniques, among which resistive ovens are used to vaporize neutral materials, later captured by the energetic plasma that will step-wise ionize them, hence giving multiply charged ion beams for accelerators. Recently, PANDORA, a novel ECR plasma trap, has been conceived to perform interdisciplinary research spanning from nuclear physics to astrophysics, where in-plasma high charge states of metallic species are demanded. However, a full knowledge on the vaporization method and on the coupling of neutral atoms with plasma and its overall dynamics is still not available. Simulations, hence, are of fundamental relevance to improve the overall efficiency, reduce consumption of rare expensive isotopes, and to improve the ion source performance. We present a numerical study about metallic species suitable for oven injection in ECRIS, focusing on metals diffusion, transport, and wall deposition under molecular flow regime. We studied the metal dynamics with and without plasma. Results underline the plasma role on a space-dependent conversion yield, reflecting the strongly inhomogeneous ECR plasma. The plasma and its parameters have been modelled using an established self-consistent particle-in-cell model. The numerical tool is conceived for the PANDORA plasma trap but can be extended to other ECR plasmas and traps. As test cases we studied the 134Cs and 48Ca radioisotopes, as metals of interest for the modern nuclear physics. A focus is given on the β-decaying 134Cs, as an application case for PANDORA, providing quantitative estimates of the γ-detection signal-poisoning effect by neutral metals deposition at the chamber wall.

Progress of the laser ion source upgrade (LION2) for RHIC and NSRL program at Brookhaven National Laboratory

At Brookhaven National Laboratory (BNL), the LION2 ion source is being constructed to replace an existing laser ion ablation ion source (LIS) at the EBIS facility, which provides heavy ion beams of multiple ion species for the operation of NASA Space Radiation Laboratory (NSRL) and Relativistic Heavy Ion Collider (RHIC). The LION1 ion source currently provides singly charged ions of Li, B, C, O, Al, Si, Ca, Ti, Fe, Cu, Zr, Nb, Ag, Tb, Ta, W, Au, Bi, and Th with a rapid-species-change capability. An electron beam ion source, Extended-EBIS captures, confines, and ionizes the ions to high charge state, suitable for injection and acceleration by an RFQ accelerator. Typically, single pulses of the LIS ion species for NSRL are changed sequentially during Galactic Cosmic Ray experiments, while multiple pulses of a given ion beam are provided quasi-simultaneously for RHIC. LION2 will have the same capability of the rapid-species-change with improved beam performance and reliability. LION2 is being constructed in a remote assembly location and is expected to finish in December 2023. The removal of LION1 and installation of LION2 is planned during the December 2023 or summer 2024 shutdown.

Permanent magnet ECR ion source and LEBT dipole for single-ended heavy ion ToF-ERDA facility

We present the status of the ion source and low energy beam transport prototyping for a single-ended heavy ion time-of-flight elastic recoil detection analysis equipment. The environmentally friendly concept is based on a permanent magnet ECR ion source and dipole magnet on a 500 kV platform without SF6 insulation, producing high charge state noble gas ion beams, e.g. 3–6 MeV argon. The ion fluxes of Ar6+–Ar12+ achieved with the CUBE-ECRIS permanent magnet minimum-B quadrupole ion source exceed 1-10 particle nA required for the low energy ToF-ERDA application. The CUBE-ECRIS can produce over 1 particle nA krypton and xenon beams up to charge states Kr19+ and Xe24+, which enables extending the scope of the ToF-ERDA application. The integration of an adjustable-field permanent magnet dipole into the CUBE-ECRIS test stand at the JYFL accelerator laboratory is described briefly.

Rest in phase transition: Should charging habits in next generation EVs be adapted?

Nickel-rich cathode materials are a popular cathode for high energy lithium ion batteries in the current and next generation of electric vehicles. While nickel-rich cathodes offer high energy density, their cycle-life is compromised due to several factors directly related to their (de)lithiation behavior. At high state of charge the nickel-rich cathode experiences a hexagonal-hexagonal transition which is accompanied by drastic changes in the unit cell parameters. This phenomenon is detrimental for cycle-life of a battery cell. This work elucidates on the effect of storing LiNi0.8Mn0.1Co0.1O2‖Graphite cells at 95 % state of charge corresponding to the above-mentioned transition for 10 h every six cycles. The results are compared to cells cycled without a rest at high state of charge and cells cycled to 100 % state of charge. Analysis of the obtained cycling data shows that resting lithium ion cells based nickel-rich cathode based cells is detrimental leading to higher impedance growth and capacity decay than cycling to 100 % state of charge.

Thermal runaway and soot production of lithium-ion batteries: Implications for safety and environmental concerns

Global energy shortages are becoming increasingly severe, and lithium-ion batteries are becoming an important substitute for fossil fuels. However, thermal runaway of a battery is a significant factor impacting battery industry development. Here, we conducted tests on battery thermal runaway using a combustion test chamber, analysing the effects of natural aging and state of charge (SOC) on battery thermal runaway. Additionally, EDS and XPS were used to analyse the soot particles formed during thermal runaway. Four stages in thermal runaway, e.g., battery bulge, smoke release, jet fire, and fire extinction. LiFePO4 with a higher SOC is more likely to cause thermal runaway. In addition, natural aging has an obvious impact on the intensity of thermal runaway. The gas products generated during a battery fire are identified as C1–C4 hydrocarbons. The soot generated by battery combustion presents a typical “core-shell” structure. The soot surface exhibits C–C, C–O, and O–H bonds, while the soot from early manufactured batteries also contains O–CO and π bonds. Soot contains not only C and O but also trace amounts of Li, F, P and Fe. These results reveal the characteristics of soot emission during thermal runaway of batteries, providing valuable insights for evaluating their toxicity and environmental impact.

The gas production characteristics and catastrophic hazards evaluation of thermal runaway for LiNi0.5Co0.2Mn0.3O2 lithium-ion batteries under different SOCs

Lithium-ion batteries (LIBs) are widely used as electrochemical energy storage systems in electric vehicles due to their high energy density and long cycle life. However, fire accidents present a trend of frequent occurrence caused by thermal runaway (TR) of LIBs, so it is especially important to evaluate the catastrophic hazards of these LIBs. This study conducted the adiabatic TR test coupled gas production test, Gas Chromatography-Mass Spectrometry test, and explosion limit test on a commercial LIB with Ni0.5Co0.2Mn0.3 as the cathode material at different states of charge (SOCs). The results show that the TR temperature and the maximum temperature at low SOC are lower compared to that at a high SOC. The probability of LIBs TR at less than SOC = 50 % is small and also causing less harm. For the gas production characteristics, the lower the SOC of the battery, the lower the gas production volume. The peak and steady-state gas production increase with the increase of SOC. For the mixed gases generated during TR, the content of CO2 shows a trend of decreasing with the increasing of battery SOC, while that of H2 and CO increase with the increasing of SOC. For the explosion limit of the mixed gas, the lower explosion limit and upper explosion limit decrease and increase with the increasing of SOC, respectively. Finally, based on the seven parameters related to the TR gas production of LIBs and so on, the analytic hierarchy process method was used to establish a LIB TR disaster-causing hazard evaluation system. The evaluation system can quantitatively evaluate the thermal safety of a LIB. This is instructive for establishing a comprehensive quantitative evaluation method for battery safety in practical engineering applications.

Structural Insights into Linkage-Specific Ubiquitin Chains Using Ion Mobility Mass Spectrometry.

The structural characterization and differentiation of four types of oligoubiquitin conjugates [linear (Met1)-, Lys11-, Lys48-, Lys63-linked di-, tri-, and tetraubiquitin chains] using ion mobility mass spectrometry are reported. A comparison of collision cross sections for the same linkage of di-, tri-, and tetraubiquitin chains shows differences in conformational elongation for higher charge states due to the interplay of linkage-derived structure and Coulombic repulsion. For di- and triubiquitin chains, this elongation results in a single narrow feature representing an elongated conformation type for multiple higher charge state species. In contrast, higher charge state tetraubiquitin species do not form a single conformer type as readily. A comparison of different linkages in tetraubiquitin chains reveals greater similarity in conformation type at lower charge states; with increasing charge state, the four linkage types diverge in the relative proportions of elongated conformer types with Met1- ≥ Lys11- > Lys63- > Lys48-linkage. These differences in conformational trends could be discussed with respect to biological functions of linkage-specific polyubiquitinated proteins.