Stabilizing a Strongly Nonlinear Structure Through Shaker Dynamics in Fixed Frequency Voltage Control Tests.
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Robbins, Eric↗
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Stabilizing a Strongly Nonlinear Structure Through Shaker Dynamics in Fixed Frequency Voltage Control Tests
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Robbins, Eric↗
Small-Signal Analysis of Current-Limiting Grid-Forming Inverters
Grid-forming (GFM) inverters are equipped with a current limiter to protect the device during grid disturbances. Because the intervention of the current limiter can compromise the transient stability of the GFM inverter, various types of current limiter designs and additional frequency-stabilization control methods have been proposed in recent literature to aid in transient GFM inverter stability; however, the small-signal stability implications of adding these additional control blocks during, in particular, off-nominal conditions are not fully understood. To address this challenge, this paper presents a generic small-signal model of a GFM inverter that incorporates various types of current limiters and frequency stability-enhancing controls. With the proposed model, we analyze the root causes of inverter instability, which reveals two critical design trade-offs. First, due to current-limiter engagement caused by a disturbance, the GFM inverter dynamics are altered, which can lead to voltage oscillations. Second, additional frequency-stabilization controls can improve the small-signal stability of the GFM inverter, but at the cost of reduced power and voltage support to the grid. Comprehensive hardware experiments validate the theoretical concept and analysis. The findings in this work underscore the importance of incorporating both transient-response and small-signal dynamics requirements into the design procedure of GFM current limiters and frequency-stabilization controls.
24 POWER TRANSMISSION AND DISTRIBUTION↗
Operation of Layered LiCoO 2 to Higher Voltages with a Localized Saturated Electrolyte
The commercialization of lithium-ion batteries started with the layered LiCoO 2 (LCO) cathode for portable electronics, but only 50% of its theoretical capacity can be used in practical cells due to detrimental surface and bulk degradations when charged to high voltages. Here we demonstrate here that the stability of electrolyte plays a critical role in the performance of LCO at high voltages by employing a localized saturated electrolyte (LSE). With a cutoff voltage of 4.5 V, LCO achieves an initial 1C discharge capacity of 176 mA h g -1 and a capacity retention of 80% over 230 cycles. Even with a cutoff voltage of 4.6 V, LCO with 2% aluminum doping displays an initial discharge capacity of 189 mA h g -1 at 1C rate with 80% capacity retention over 137 cycles. With extensive analytical characterization, we show that the improved cycling stability stems from a suppression of the O3 to H1-3 phase transition as well as a robust inorganic-rich cathode-electrolyte interphase (CEI) facilitated by the LSE. This work highlights the importance of protecting the surface as well as the bulk with appropriate electrolytes for the high-voltage, higher-energy-density operation of LCO.
25 ENERGY STORAGE↗
Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization
Lithium (Li) pulverization and associated large volume expansion during cycling is one of the most critical barriers for the safe operation of Li-metal batteries. Here, we report an approach to minimize the Li pulverization using an electrolyte based on a fluorinated orthoformate solvent. The solid–electrolyte interphase (SEI) formed in this electrolyte clearly exhibits a monolithic feature, which is in sharp contrast with the widely reported mosaic- or multilayer-type SEIs that are not homogeneous and could lead to uneven Li stripping/plating and fast Li and electrolyte depletion over cycling. The highly homogeneous and amorphous SEI not only prevents dendritic Li formation, but also minimizes Li loss and volumetric expansion. Furthermore, this new electrolyte strongly suppresses the phase transformation of the LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode (from layered structure to rock salt) and stabilizes its structure. In conclusion, tests of high-voltage Li||NMC811 cells show long-term cycling stability and high rate capability, as well as reduced safety concerns.
25 ENERGY STORAGE↗
Trace doping of multiple elements enables stable battery cycling of LiCoO 2 at 4.6 V
LiCoO 2 is a dominant cathode material for lithium-ion (Li-ion) batteries due to its high volumetric energy density, which could potentially be further improved by charging to high voltages. However, practical adoption of high-voltage charging is hindered by LiCoO 2 ’s structural instability at the deeply delithiated state and the associated safety concerns. Here, we achieve stable cycling of LiCoO 2 at 4.6 V (versus Li/Li+) through trace Ti–Mg–Al co-doping. Using state-of-the-art synchrotron X-ray imaging and spectroscopic techniques, we report the incorporation of Mg and Al into the LiCoO 2 lattice, which inhibits the undesired phase transition at voltages above 4.5 V. We also show that, even in trace amounts, Ti segregates significantly at grain boundaries and on the surface, modifying the microstructure of the particles while stabilizing the surface oxygen at high voltages. These dopants contribute through different mechanisms and synergistically promote the cycle stability of LiCoO 2 at 4.6 V.
25 ENERGY STORAGE↗
Evaluation of Optimal Net Load Management in Microgrids Using Hardware-in-the-Loop Simulation
This paper presents the performance evaluation of a net load management (NLM) engine that balances load and generation in an isolated community to power a critical facility after a grid interruption event (e.g., the loss of a large generation unit). This NLM engine is particularly important for microgrid systems because it provides a high-speed, cost-optimal control solution to coordinate grid-forming inverters and to dispatch grid-following inverters and deferrable loads in microgrid systems to enhance grid resilience and reliability. The NLM algorithm cost-optimally dispatches the grid-following inverters and deferrable loads based on the demanded power and load priorities, and the grid-forming inverters use droop control to form system voltages and share active and reactive power. A controller-hardware-in-the-loop platform is developed to evaluate the control performance of the NLM algorithm with two sequential contingency events of lost generation units. The experimental results indicate that the NLM engine can maintain system stability, achieve the targeted system voltage and frequency, and balance load and generation to serve the critical facility with improved system resilience and reliability.
grid-following inverter↗
Evaluation of Optimal Net Load Management in Microgrids Using Hardware-in-the-Loop Simulation
This presentation discusses the performance evaluation of a net load management (NLM) engine that balances load and generation in an isolated community to power a critical facility after a grid interruption event (e.g., the loss of a large generation unit). This NLM engine is particularly important for microgrid systems because it provides a high-speed, cost-optimal control solution to coordinate grid-forming inverters and to dispatch grid-following inverters and deferrable loads in microgrid systems to enhance grid resilience and reliability. The NLM algorithm cost-optimally dispatches the grid-following inverters and deferrable loads based on the demanded power and load priorities, and the grid-forming inverters use droop control to form system voltages and share active and reactive power. A controller-hardware-in-the-loop platform is developed to evaluate the control performance of the NLM algorithm with two sequential contingency events of lost generation units. The experimental results indicate that the NLM engine can maintain system stability, achieve the targeted system voltage and frequency, and balance load and generation to serve the critical facility with improved system resilience and reliability.
droop control↗
Introduction to Grid Forming Inverters: A Key to Transforming our Power Grid [Slides]
A grid-forming (GFM) inverter-based resource (IBR) controls maintain an internal voltage phasor that is constant or nearly constant in the sub-transient to transient time frame. This definition means that the GFM IBR will nearly immediately respond to changes in the external system and attempt to maintain IBR control during challenging network conditions to maintain grid stability. In GFM IBR, the voltage phasor is controlled to maintain synchronism with other devices in the grid while regulating the active and reactive power appropriately to support the grid. This contrasts with conventional GFL IBR controls wherein immediately after a disturbance (0-5 cycles), within the normal operating range of voltage, the output current phasor magnitude and angle remain unchanged, and the current phasor begins changing only within the transient time frame (tens of cycles) to strictly control the active and reactive power being injected into the network. This presentation gives an introduction to GFM IBR and presents the current state of the art in this area.
24 POWER TRANSMISSION AND DISTRIBUTION↗
Molecular Engineering to Enable High-Voltage Lithium-Ion Battery: From Propylene Carbonate to Trifluoropropylene Carbonate
Molecular engineering of electrolyte structures has led to the successful application of trifluoropropylene carbonate (TFPC), a fluorinated derivative of propylene carbonate (PC), in next-generation high-voltage high-energy lithium-ion cell. Additionally, in contrast to a PC-based electrolyte which cointercalates in the form of Li + -solvated species into the graphene layer and exfoliates a graphite anode, a TFPC-based electrolyte is highly compatible with a graphite anode at low potential. Additionally, it shows exceptional oxidation stability on the charged cathode surface owing to the presence of the -CF 3 group. An all-fluorinated electrolyte, that is, 1.0 M LiPF 6 TFPC/2,2,2-trifluoroethyl carbonate (FEMC) (1/1 volume ratio) + FEC additive, was formulated and demonstrated excellent cycling stability in a high-voltage LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite cell cycled between 3.0 and 4.6 V.
25 ENERGY STORAGE↗
Structure and Interface Design Enable Stable Li-Rich Cathode
Li-rich layered-oxide cathodes have the highest theoretical energy density among all the intercalated cathodes, which have attracted intense interests for high energy Li-ion batteries. However, O3-structured layered-oxide cathodes suffer from a low initial Coulombic efficiency (CE), severe voltage fade, and poor cycling stability because of the continuous oxygen release, structural rearrangements due to irreversible transition-metal migration, and serious side reactions between the delithiated cathode and electrolyte. In this work, we report that these challenges are migrated by using a stable O2-structured Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 (O2-LR-NCM) and all-fluorinated electrolyte. The O2-LR-NCM can restrict the transition metals migrating into the Li layer and the in situ formed fluorinated cathode electrolyte interphase (CEI) on the surface of the O2-LR-NCM from the decomposition of all-fluorinated electrolyte during initial cycles effectively restrains the structure transition, suppresses the O2 release, and thereby safeguards the transition metal redox couples, enabling a highly reversible and stable oxygen redox reaction. O2-LR-NCM in all fluorinated electrolytes achieves a high initial CE of 99.82 % and cycling CE of and cycling CE of >99.9%, high reversible capacity of 278 mAh/g, and high capacity retention of 83.3% after 100 cycles. The synergic design of electrolyte and cathode structure represents a promising direction to stabilize high-energy cathodes.
25 ENERGY STORAGE↗
Influence of solvents on electrochemical stability window of ionic liquid solutions
The electrochemical stability window (ESW) defines the voltage range within which an electrolyte remains stable against oxidation and reduction, serving as a key descriptor for ionic liquid (IL)-based systems. The ESWs of 15 ILs with diverse cation-anion combinations were systematically investigated, both in their neat forms and as binary mixtures with three representative solvents, i.e., propylene carbonate (PC), ethylene glycol (EG), and tetrahydrofuran (THF). Cyclic voltammetry on a glassy carbon electrode determined anodic and cathodic stability limits, revealing that ESW protection in IL-solvent mixtures strongly depends on solvent polarity, proticity, and IL compatibility. PC, with a high dielectric constant and aprotic character, broadened anodic limits and moderately stabilized cathodic limits. THF maintained compact interfacial structure, offering additional cathodic protection, whereas EG, being protic, reduced ESWs via proton-coupled electron transfer and hydrogen evolution. The solvent protection trend followed by PC > THF > EG, with bulky, hydrophobic cations ([HMIM] + , [BMPYRR] + ) and weakly coordinating anions ([NTF 2 ] - , [DCA] - , [DEP] - ) showing the highest ESW protection for 50 mol% IL in these solvents. Among the neat ILs, [EMIM][DEP], [HMIM][PF 6 ], and [BMPYRR][DCA] showed wide ESWs of ∼5.5 V. These results provide valuable insight into solvent-modulated electrochemical stability, enabling rational design of IL-based electrolytes for energy storage and electrosynthesis.
25 ENERGY STORAGE↗
Structural Stabilization of P2-type Sodium Iron Manganese Oxides by Electrochemically Inactive Mg Substitution: Insights of Redox Behavior and Voltage Decay
Layered P2-type Na 0.8 Mn 0.5 Fe 0.5 O 2 cathode material is a promising candidate for next-generation sodium-ion batteries due to the economical and environmentally benign characteristics of Mn and Fe. The poor cycling stability of the material, however, is still a problem that must be solved. To address the problem, here, electrochemically inactive Mg 2+ was introduced into the structure by substituting some of the Fe ions. It was shown that Mg substitution led to a smoother voltage profile with improved cycling performance and rate capability. These observations were attributed to the suppressed structural changes during electrochemical processes. Detailed redox mechanisms, associated local structural changes, and phase transitions were investigated by X-ray absorption spectroscopy and X-ray diffraction. From the detailed analysis of electrochemical behaviors, it was also identified how the redox reactions and structural disordering occurred in the high-and low-voltage regions and how Mg substitution stabilized the structure.
25 ENERGY STORAGE↗
Critical Insights into Solvent Choice for High-Voltage Organosulfur Electrolytes
Organosulfur electrolytes are promising candidates for enabling high-voltage cathodes due to their superior oxidative stability compared to conventional carbonate-based systems. However, their viscous nature and inability to passivate the anode necessitate the use of passivating agents and diluents to achieve meaningful charge/discharge rates. In this study, we investigate the use of cyclic fluorinated carbonates (CFCs) to form passivating interphases on electrode surfaces, aiming to optimize electrolyte performance in high-voltage systems. Electrolyte formulations containing 1.2 M LiPF 6 in a CFC:sulfone:1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TTE) mixture (2/5/3 V/V/V) were assessed in full-cell configurations with a LiNi 0.8 Mn 0.1 Co 0.1 O 2 (FCG-NMC) cathode and a 4.5 V upper cutoff potential. The results reveal that 3-3-3-trifluoropropylene carbonate (TFPC) combined with ethyl methyl sulfone (EMS) optimizes electrolyte performance, resulting in lower resistance buildup and reduced capacity loss compared to commercial electrolytes. We also explore the failure mechanisms of several carbonate/sulfone mixtures and identify key considerations for electrolyte compatibility in high-voltage systems. TFPC enhances cycling stability and lowers overall cell resistance, while fluoroethylene carbonate (FEC) formulations, despite higher ionic conductivity, fail to form adequate passivation layers, leading to rapid capacity loss. Additionally, EMS provides superior physical properties that avoid common failure modes seen with other sulfone solvents like methyl isopropyl sulfone and tetramethylene sulfone. Furthermore, this study underscores the importance of carefully selecting passivating carbonates and sulfone solvents to improve electrolyte performance and expand the viability of high-voltage electrolyte systems.
LiNi0.8Mn0.1Co0.1O2 cathode↗
Design of Next-Gen Cathode Materials With Both Cation and Anion Redox
Among all candidates of positive electrode materials for lithium ion batteries, the lithium rich layered oxides have gained growing research interests in recent years. Their energy density can reach closely to 700-900Wh/g (at materials level), making them the positive electrode materials with highest energy density among all known intercalation compounds for cathode materials. Combining both first principles computation, advanced electron and X-ray based imaging, we demonstrated that in the Li-rich materials oxygen vacancies are present and assist the transition metal ion migration through a facile mechanism. This means it is critically important to control the oxygen activities in these compounds for high voltage operations. In addition, the NiMn spinel oxides show little oxygen activities and under optimized synthesis condition the electrolyte/electrode interface showed superior stability. Combining the strengths of materials synthesis and the advanced characterization, I will discuss in details the strategies for stabilizing the anion redox for higher voltage electrode materials for lithium ion batteries.
Meng, Ying Shirley↗
Experimental performance of a 1-kilowatt arcjet thruster
A formerly unused cathode and anode/nozzle assembly from a flight model arcjet was tested with nitrogen, hydrogen, and nitrogen-hydrogen mixture simulating ammonia decomposition products at arc power levels from about 300 to 950 W. Two different power sources and two nozzle configurations were tested at low back-ground pressures to exclude facility effects. Increased nozzle expansion ratio improved cold flow nozzle efficiency from 0.8 to 0.9. Hydrogen thrust efficiency of 0.26 at 872 sec specific impulse matched some 1964 performance on a similar device. Simulated ammonia thrust efficiency was 0.31 at 422 sec. Spontaneously occurring voltage mode changes at constant arc current could be partially stabilized with appropriate power source characteristics. In the higher voltage mode specific impulse was higher, but thrust efficiency changed only slightly from that of the lower voltage mode. Sustained tests of up to 2 hr duration exhibited no apparent performance degradation with time.
Nakanishi, S.↗
Experimental performance of a 1-kilowatt arcjet thruster
A formerly unused cathode and anode/nozzle assembly from a flight model arcjet was tested with nitrogen, hydrogen, and nitrogen-hydrogen mixture simulating ammonia decomposition products at arc power levels from about 300 to 950 W. Two different power sources and two nozzle configurations were tested at low background pressures to exclude facility effects. Increased nozzle expansion ratio improved cold flow nozzle efficiency from 0.8 to 0.9. Hydrogen thrust efficiency of 0.26 at 872 sec specific impulse matched some 1964 performance on a similar device. Simulated ammonia thrust efficiency was 0.31 at 422 sec. Spontaneously occurring voltage mode changes at constant arc current could be partially stabilized with appropriate power source characteristics. In the higher voltage mode specific impulse was higher, but thrust efficiency changed only slightly from that of the lower voltage mode. Sustained tests of up to 2 hr duration exhibited no apparent performance degradation with time.
Nakanishi, S.↗
Achieving Thermodynamic Stability of Single-Crystal Co-Free Ni-Rich Cathode Material for High Voltage Lithium-Ion Batteries
Ni-rich layered cathode materials are progressively considered as the standard configuration of high-energy electric vehicles by virtues of their high capacity and eliminated “range anxiety.” However, the poor cyclic stability and severe cobalt supply crisis would restrain their wide commercial applicability. Here, a cost-effective single-crystal Co-free Ni-rich cathode material LiNi 0.8 Mn 0.18 Fe 0.02 O 2 (NMF), which outperforms widely commercial polycrystalline LiNi 0.83 Co 0.11 Mn 0.06 O 2 (MNCM) and single-crystal LiNi 0.83 Co 0.11 Mn 0.06 O 2 (SNCM) is reported. Surprisingly, NMF can compensate for the reversible capacity loss under the designed conditions of high-temperature and elevated-voltage, achieving a competitive energy density compared with conventional MNCM or SNCM. Further, combining operando characterizations and density functional theory calculation, it is revealed that NMF cathode with improved dynamic structure evolution largely alleviates the mechanical strain issue commonly found in Ni-rich cathode, which can reduce the formation of intragranular cracks and improve the safety performance. Consequently, this new Co-free NMF cathode can achieve a perfect equilibrium between material cost and electrochemical performance, which not only reduces the production cost by >15%, but also demonstrates excellent thermal stability and cycling performance.
25 ENERGY STORAGE↗