Degradation Mechanism Research Articles

A TEM Study of Structural Degradation in LiFePO4 Batteries after Hybrid Vehicle Use

Establishing a robust, efficient circular economy for batteries hinges on understanding how they decay over time under various conditions. This understanding is crucial to maximize material use before recycling or disposal. A key aspect of this endeavor is the study of lithium iron phosphate (LiFePO4), a pivotal battery technology whose structural integrity over time remains a subject of inquiry.1 Known aging mechanisms in LiFePO4 (LFP) batteries include electrode degradation, SEI growth, and electrolyte decomposition.1 These processes extend to the cathode, where degradation can manifest as Fe dissolution, Li inventory loss, Fe/Li anti-site defects, and LFP amorphization.1–3 However, these mechanisms are typically studied in lab-aged cells under controlled conditions, leaving a gap in our understanding of their behavior in real-life, commercialized applications.Our research aims to bridge this gap by characterizing the degradation mechanisms of LFP cathode material in various states of health (SOH) after use in a hybrid vehicle. We sourced our cathode samples from 26650 cells extracted from a BAE ESS-A123 hybrid bus battery pack. After selecting cells with drastically different SOHs based on previous analyses,4 we employed transmission electron microscopy (TEM) for detailed characterization.In this talk, we will share insights gained from high-resolution TEM characterization, alongside chemical analysis using energy-filtered TEM and electron energy loss spectroscopy (EELS). Our focus will be on changes in the olivine structure, including lattice parameter alterations, Li and Fe migration, and Fe oxidation. By combining cell-level SOH analyses with TEM characterization, we will highlight how electrochemical test results correlate with material degradation mechanisms, enhancing our understanding of battery health, longevity, and diagnostics. Wang, L. et al. Insights for understanding multiscale degradation of LiFePO4 cathodes. eScience 2, 125–137 (2022). Li, X. et al. First Atomic-Scale Insight into Degradation in Lithium Iron Phosphate Cathodes by Transmission Electron Microscopy. J. Phys. Chem. Lett. 11, 4608–4617 (2020). Xu, P. et al. Efficient Direct Recycling of Lithium-Ion Battery Cathodes by Targeted Healing. Joule 4, 2609–2626 (2020). Ramirez-Meyers, K., Rawn, B. & Whitacre, J. F. A statistical assessment of the state-of-health of LiFePO4 cells harvested from a hybrid-electric vehicle battery pack. J. Energy Storage 59, 106472 (2023).

Reconstructing the Pseudo-2-Dimensional (p2D) Model in Comsol Multiphysics Using Mathematical Interfaces

The classic ‘pseudo-2-dimensional’ (p2D) model of Newman and co-workers (also known as the DFN model), with its different efficient implementations, is the state-of-the-art physics-based electrochemical model for lithium-ion batteries. COMSOL Multiphysics (COMSOL) is a popular modeling software for multiphysics simulations, and its Battery Design Module for Li-ion batteries is widely used in the battery modeling community. This work presents a step-wise model development for reconstructing the detailed p2D model equations. This includes variable model parameters and weak-form implementation for the solid-phase diffusion, eliminating the need for non-local couplings and approximations for modeling the pseudo radial-dimension in the solid-phase.To model and understand the effect of capacity degradation on lithium-ion cells, the battery models in COMSOL need to incorporate additional degradation mechanisms. In this work, we have followed the approach of equation-based modeling in COMSOL, which enables us to formulate the p2D model using the mathematical PDE interfaces. This approach provides us with a lot of flexibility in terms of battery degradation model formulation and helps develop a clearer understanding of the p2D model equation in light of the assumptions involved.The steps in the model development involved writing the conservation equations in the generic mathematics interfaces coupled with the additional equations for the degradation mechanisms. The efforts were centered on developing cycling simulations based on Events for practically relevant operating conditions. This custom model was validated against the results from COMSOL’s Battery Interface, in-house codes, and baseline cycle data from the experiments and further developed as a physicochemical degradation model for automotive, large-format Lithium-ion batteries.This equation-based COMSOL model with cycling works without the requirement for Battery Design Module, LiveLink and Application Builder and can be adopted for a variety of electrochemical modeling applications by the electrochemical modeling community.

High Efficiency and High Durability Proton Exchange Membrane Water Electrolyzers for Hydrogen Production with Advanced Catalyst Coated Membranes

Water electrolyzers and fuel cells can be used to create a closed loop system for space exploration. Electrolyzers allow for reliable self-sustainable generation of hydrogen and oxygen for energy storage, followed by conversion into electrical energy in a fuel cell. A first-order safety concern for water electrolyzer operation is hydrogen crossover. Transport of hydrogen to the oxygen rich anode in proton exchange membrane (PEM) water electrolyzers poses safety concerns when the hydrogen concentration in the anode flow field approaches the hydrogen lower flammability limit (LFL). Hydrogen storage efficiency relies on high hydrogen pressure, leading to pressure-driven hydrogen crossover. Mitigation of hydrogen crossover through research and development of a platinum metal recombination layer has been demonstrated in high performing, durable PEMWEs.1-4 Ouimet4 explored the use of a novel dual recombination layer configuration to mitigate PEM water electrolyzer hydrogen crossover. In addition, the current state of the art for PEM fuel cells and water electrolyzers rely on perfluoro-sulfonated acid (PSFA) based membranes. There are significant challenges facing the use of PSFA-based membranes; namely, environmental contamination and performance limitations. The use of a hydrocarbon membrane allows for the development of a PSFA-free system that shows higher efficiency and durability. Investigation of hydrocarbon membranes pave way for developing a PEM water electrolyzer that will demonstrate improved gas permeability resistance, mechanical strength, and thermal stability.5-8 There is a need for both hydrogen crossover mitigation strategies and durability testing with hydrocarbon membranes.The research outlined in this work is focused on the development of PSFA-free PEM water electrolyzers with low hydrogen crossover. In this work, the dual recombination layer configuration will be incorporated into a hydrocarbon membrane for PEM water electrolysis. Polarization, electrochemical impedance spectroscopy, electrochemical equivalent circuits, distribution of relaxation times, and materials characterization will be used to investigate the cell performance and durability. References G. Mirshekari, R. Ouimet, Z. Zeng, H. Yu, S. Bliznakov, L. Bonville, A. Niedzwiecki, C. Capuano, K. Ayers, and R. Maric, “High-performance and cost-effective membrane electrode assemblies for advanced proton exchange membrane water electrolyzers: Long-term durability assessment,” international journal of hydrogen energy, vol. 46, no. 2, pp. 1526–1539, 2021.Z. Zeng, R. Ouimet, L. Bonville, A. Niedzwiecki, C. Capuano, K. Ayers, A. P. Soleymani, J. Jankovic, H. Yu, G. Mirshekari, et al., “Degradation mechanisms in advanced meas for pem water electrolyzers fabricated by reactive spray deposition technology,” Journal of The Electrochemical Society, vol. 169, no. 5, p. 054536, 2022.A. Martin, D. Abbas, P. Trinke, T. Böhm, M. Bierling, B. Bensmann, S. Thiele, and R. Hanke-Rauschenbach, “Communication—proving the importance of ptinterlayer position in pemwe membranes for the effective reduction of the anodic hydrogen content,” Journal of The Electrochemical Society, vol. 168, no. 9, p. 094509, 2021.R. J. Ouimet, “Catalyst development by a novel fabrication process for energy applications,” University of Connecticut Doctoral Dissertation, 2021.P. Trinke, P. Haug, J. Brauns, B. Bensmann, R. Hanke-Rauschenbach, and T. Turek, “Hydrogen crossover in pem and alkaline water electrolysis: mechanisms, direct comparison and mitigation strategies,” Journal of The Electrochemical Society, vol. 165, no. 7, p. F502, 2018.P. Trinke, B. Bensmann, and R. Hanke-Rauschenbach, “Current density effect on hydrogen permeation in pem water electrolyzers,” International Journal of Hydrogen Energy, vol. 42, no. 21, pp. 14355–14366, 2017.H. Q. Nguyen and B. Shabani, “Proton exchange membrane fuel cells heat recovery opportunities for combined heating/cooling and power applications,” Energy Conversion and Management, vol. 204, p. 112328, 2020.C. Klose, T. Saatkamp, A. Münchinger, L. Bohn, G. Titvinidze, M. Breitwieser, K. D. Kreuer, and S. Vierrath, “All-hydrocarbon mea for pem water electrolysis combining low hydrogen crossover and high efficiency,” Advanced Energy Materials, vol. 10, no. 14, p. 1903995, 2020.

(Invited) Self-Discharge of Layered Oxide Cathodes Induced by Carbonate-Mediated Hydrogenation

Significant efforts have been made to improve the energy and power characteristics of cathodes in Li-ion batteries, while the research into cathode self-discharge has lagged behind. Self-discharge is the voltage drop experienced by all rechargeable batteries while stored in the charged state. The voltage drop becomes more problematic with increased cathode voltage and temperature. The physicochemical nature of internal reactions leading to cathode self-discharge is hardly understood and seldom discussed.To tackle this challenge, the structure and redox evolution of commercial LiNi0.5Mn0.3Co0.2O2 electrodes and single crystal cathode thin films upon the self-discharge in carbonate-based electrolyte is revealed by surface-sensitive X-ray scattering, spectrometric and electrochemical characterizations in conjunction with thermodynamic analysis. As evidenced by the interfacial toolkits and theoretical calculations, there is an evolution and growth of cathode surface reduction layer in different types of electrolyte after self-discharged from different potentials. Structural and chemical chacterizations as well as the elemental depth profiles within cathode thin film confirms proton-insertion-induced layered cathode hydrogenation. Calculation shows that such process is both thermodynamically and kinetically favorable and is triggered by the interfacial hydrogen atom abstraction of methylene group in carbonate solvent on delithiated cathode surface. A combination of experimental and theoretical studies reveals the carbonate-mediated cathode hydrogenation mechanism accounting for the voltage drop in the self-discharge. This offers additional understanding regarding defect generation and the degradation mechanism in layered cathodes beyond the traditional behaviors of lithium-diffusion-induced self-discharge and rock-salt phase induced cathode degradation. This study offers foundational knowledge of the interfacial degradation of cathode that can be translated to the rational design of improved cathodes and electrolytes, and the self-discharge mechanism studies in other electrochemical ion insertion materials and devices.

Understanding the Degradation Mechanism for NiMo Composite and Effect of Ionomer on the Activity Towards HER

Hydrogen is an essential commodity for achieving cleaner and greener energy.1,2 Due to its high gravimetric energy density, hydrogen is favored as a carbon-neutral fuel.2,3 Moreover, the electrochemical accessibility of hydrogen evolution and oxidation reactions enable hydrogen to be used as a reversible fuel, as in hydrogen battery anodes and unitized reversible fuel cells.4,5 Platinum group metals (PGMs) are excellent catalyst for hydrogen chemistry, as they exhibit negligible activation barrier for HER and HOR, but they are costly and the upstream processes for mining and purification are unsustainable.6 A promising alternative to PGM catalysts would be nonprecious transition metal alloys/composites in form of nanoparticles. These materials are more readily available and lower in cost. Nonetheless, non-precious catalysts developed to date have never met the benchmarks set by PGMs in terms of catalytic activity and stability.Our lab is continuing a long-running effort to develop and improve nickel-molybdenum (Ni–Mo) composites, which stand as one of the strongest candidates for non-PGM HER and the HOR. In prior work, we developed a method to synthesize Ni–Mo nanoparticles supported on oxidized carbon, which increases catalyst dispersion and significantly reduces losses due to interfacial resistivity.7 The catalyst composite has a core@shell structure, where in the core is mainly nickel-rich alloy and the shell is primarily molybdenum-rich oxide.Furthermore, DFT calculations suggest the addition of Mo in the catalyst subsurface weakens hydrogen binding to surface Ni sites, thus increasing the overall activity toward HER/HOR.8 In ongoing work to further develop Ni–Mo/C composites, we are focusing on catalyst degradation under storage and operating conditions. To examine catalyst durability upon extended storage, we measured activity toward hydrogen evolution progressively for a single batch of catalyst powdered retained at room temperature in an aerobic environment over 850 hours. We observed a monotonic decrease in catalytic activity culminating in a >90% decrease in activity. Post-mortem analysis via XRD showed the increased peak intensities corresponding to NiO and MoO3. We further observed that the catalyst remains active over extended periods when stored under a dry, oxygen-free atmosphere. Finally, exposing the degraded catalyst to thermal reduction increased catalytic activity. Together, these results strongly suggest aerobic oxidation as the primary degradation mechanism under shelf-storage, with straightforward mitigations steps readily available by excluding air and water. This finding further suggests that oxide component of the synthesized catalyst is not an active site for hydrogen chemistry, although we speculate that some surface oxide is beneficial for enhancing the rate of water dissociation.9 We also studied the impact of the ionomer chemistry on the catalytic activity of Ni–Mo composites for alkaline anion exchange membrane (AEM) electrolyzer applications. Surprisingly, we observed an ~80% reduction in catalytic activity for Ni–Mo composites formulated into thin film HER catalysts using poly(aryl piperidinium) (PAP) carbonate AEM ionomers relative to control samples based on Na-exchanged Nafion ionomer binders. Further work showed this result was specific to the carbonate form of the ionomer, as HER activity was fully recovered when we used halide forms of the PAP ionomer. Work is ongoing to establish the physicochemical basis of this poisoning effect.Based on these findings, we developed functional AEM electrolyzer assemblies with IrOx anodes and Ni–Mo/C cathodes, where the cathode composition was formulated based on our best results from RDE studies. These MEAs yielded electrolyzer performance properties that were indistinguishable from MEAs we tested using Pt–Ru/C cathodes that were otherwise identical in composition.8 This leads us to conclude that advanced Ni–Mo/C catalyst composites can indeed achieve performance parity with PGM catalysts on the basis of initial catalytic activity, whereas significant work remains to characterize durability under extended operating conditions.

Investigating Cobalt Degradation in Acidic Environments for Oxygen and Hydrogen Electrocatalysis with Time-Resolved Mass Spectrometry Techniques

Cobalt is an important additive within commercially available energy devices including hydrogen fuel cell vehicles, lithium-ion batteries for electric vehicles and portable devices, and electrolyzers for water splitting. Regarding devices that include a proton exchange membrane (PEM), such as proton exchange membrane fuel cells (PEMFCs) and proton exchange membrane water electrolyzers (PEMWEs), cobalt-based materials are commonly used to perform the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER), respectively. However, given the acidic environment induced by the PEM (pH = 1), cobalt is thermodynamically unstable at ORR and HER relevant potentials, which results in cobalt dissolution and consequently decreases in device performance and lifetime. Minimizing electrode degradation of cobalt-based materials in acidic environments therefore requires a holistic understanding of cobalt’s degradation mechanisms, as it would be necessary to simultaneously monitor electrochemical output (current/voltage), cobalt dissolution, and product formation, which is not possible with one technique alone. To gain such an understanding, in this presentation I will discuss our work on developing comparable time-resolved techniques such as on-line inductively coupled plasma mass spectrometry (ICP-MS) and electrochemical mass spectrometry (EC-MS) to investigate the relationship between applied potential, time, cobalt dissolution, and product formation.With usage of EC-MS, it was observed that cobalt is active for HER in 0.1 M HClO4. and undergoes little to no cobalt dissolution (< 1 ng s-1) at potentials where cobalt is evolving H2 per ICP-MS measurements. This suggests that cobalt stability in acid strongly coincides with hydrogen evolution. In addition, when comparing cobalt’s material stability from the on-line ICP-MS experiments with its thermodynamic stability from its Pourbaix diagram, there is little to no cobalt dissolution at potentials outside its thermodynamic stability window. This is unexpected, as cobalt is projected to be thermodynamically stable only at potentials less than -0.277 VRHE (Co2+/Co = -0.277 VRHE for a dissolved total metal ion concentration of 1 M at pH = 1), whereas our data shows that cobalt dissolution is suppressed until -0.05 VRHE. Through combining findings from both EC-MS and ICP-MS, we have postulated a stability mechanism related to surface hydrogen coverage on cobalt that can be used to explain why cobalt is stable during HER and at potentials it is thermodynamically expected to be unstable.In addition to cobalt being HER active, we also uncovered its activity for ORR in O2 saturated 0.1 M HClO4. Cobalt dissolution under O2 versus N2 saturated 0.1 M HClO4 was then compared, and it was observed that in the presence of O2, cobalt dissolution occurs faster (~3x more dissolution), likely due to O2 induced chemical dissolution. However, after 3 cycles, the observed cobalt dissolution rates under both gas types are equivalent (~225 ng s-1), indicating an important relationship between time, potential, and electrochemical environment. Altogether, this work showcases how time-resolved techniques such as ICP-MS and EC-MS can be connected to unravel stability mechanisms of materials and motivative future studies to apply a holistic approach when evaluating material stability.

Extending an Empirical Degradation Model for Li-Ion Batteries into Second-Life Applications

Lithium-ion batteries have been used increasingly in recent years for a wide range of applications, e.g., electric vehicles and large-scale power grids. Lithium-ion batteries suffer from degradation caused by their operation and their exposure to environmental conditions and thus have a limited lifetime within their first application. These batteries might be available for re-use in a different application, commonly under more moderate usage conditions. The influence of such a change in operating conditions on battery degradation within a second life application is not very well understood. Here we present the extension of an empirical degradation model that formulates the degradation process as a function of battery operations for both, first- and second life applications.Our extended semi-empirical model for battery degradation is based on work of Xu et al. [1] and combines the degradation mechanism due to the growth of the SEI layer and the degradation depth obtained in dedicated ageing tests. Within this work we focus on a commercial 64 Ah NMC-graphite pouch cell. The model parametrization is based on a large dataset containing both calendar and cycle life data of more than 100 cells, covering a large window of temperatures (5-45 °C), C-rates (0.2-1.5 C), SoC windows, and average SoC.Figure 1(a) shows the variations of state of health (SoH) with the number of the full equivalent cycle (FEC) for four cells cycling at the same constant ageing conditions (0.75C, 25°C, and 0-100% SoC). Figure 1(b) shows the fitting results of the empirical degradation model using the data from the ageing tests. It is assumed that the SEI layer model parameters are constant for this specific cell. The degradation depth increases linearly with cycle number, where the degradation rate varies with the battery operation condition. The degradation of the battery cell depends not only on external stress factors such as temperature, SoC, DoD, C-rate, but also its previous ageing history. The formation of the SEI film contributes non-linearly to the battery degradation, while the contribution of the degradation rate of different stress factors can be accounted for linearly. The degradation rate depends on the ageing modes: calendar or cycle ageing. Calendar ageing reflects the inherent degradation over time and the rate is affected by temperature and SoC. The calendar degradation rate per time unit can be obtained as a function of temperature and SoC [2, 3]. The cycle SoC window can be interpreted using DoD and mean SoC. The cycle degradation rate per FEC can be estimated as a function of temperature, mean SoC, and DoD [3]. Data-driven models and empirical correlations are applied to obtain battery degradation rate functions. The total degradation depth can be estimated by summarizing the degradation caused by the calendar ageing and the degradation resulting from all cycles.To verify the performance of the empirical degradation model, a dynamic ageing test was designed, including both calendar and cycle ageing. The historical data of SoC and temperature are shown in Figures 2 (a) and 2(b), respectively. Through analyzing the time series data of cell SoC, all cycle information can be obtained to calculate the cycle ageing. The calendar ageing was calculated based on time duration for each cycle, and the average temperature and SoC. Using the correlations for the degradation rates, the degradation depth during for each cycle can be evaluated. The accumulated degradation depth can be used to estimate the change of remaining capacity with time. Figure 2(c) shows the comparison of the prediction of SoH with the experimental data.When moving into the 2nd life regime, degradation mechanisms and their interplay become more complex, leading to a larger statistical variation in ageing rates between individual cells (i.e., see time offset in Fig 2c). This can be accounted for by readjustment of the model’s initial 2nd life SoH to the last SoH from the first life application data, as well as including statistical variation into the model’s parameters.

The Effect of Water Quality on PEM Electrolyzer Performance

There has been growing interest in the use of removable, clean, and sustainable energy sources as a solution to eliminate environmental problems caused by fossil fuels. In particular, the electrolysis of water to produce green hydrogen is one of the most promising technologies. Among various electrolysis techniques, proton exchange membrane water electrolyzer (PEMWE) stands out as the most promising for mobility and large-scale energy-storage applications (1). Hydrogen production by PEMWEs requires approximately 45 kg of high-quality water to produce 5 kg of hydrogen. It has been estimated that about 22% of the total cost of a state-of-the-art PEMWE system is for water deionization treatment (2). This water purity requirement is not only an economic barrier, but also a constraint for the use of this system in areas where high-quality water is not accessible or in areas where water for human consumption is a scarce resource. Therefore, studying the effect of water quality on PEMWE performance is an important first step in identifying key degradation mechanisms on the path to discovering new PEMWE architectures that are more tolerant of poor-quality feed waters.In this work, the effect of common impurities, such as Na+ and Mg2+, in feed water on the performance of common PEMWE architectures is studied. The main goals of the work are: 1) to understand the tolerance range for long term operation, 2) to identify major degradation mechanisms when the failure occurs. Experiments were carried out in an electrolyzer equipped with platinized Ti electrodes, IrO2 and Pt/C as anodic and cathodic catalysts, respectively, and a 115 Nafion® membrane. Durability studies of 100-hour duration and electrochemical characterization of the electrolyzer at different time intervals (polarization curves and impedance spectroscopy) were performed. The membrane/electrode assembly was probed by SEM /EDX before and after the experiments and cation concentrations in the water were monitored by ICP. An electrochemical model is proposed to explain the observed behavior of the electrolyzer with DI water and in the presence of impurities.The results show that the presence of cations affects the performance of the electrolyzer at different levels depending on the concentration of the cation and its valence (Mg2+ > Na+ >DI water). Mg+2 had the same effect as Na+ even at 5 times lower concentration. Cations have higher affinity than protons for sulfonic acid groups (-SO3 -), leading to a displacement of protons and a consequent reduction in the membrane proton conductivity. However. according to the polarization curves, there are effects beyond the ohmic potential due to the increase in membrane resistance. The major effect of cations is on the reaction kinetics, which is the primary reason for the observed increase in cell voltage. The presence of cations within the membrane blocks the transport of protons, which creates a lack of protons at the cathode, resulting in the kinetic change from proton reduction to reduction of water. Moreover, the EDX results showed that Na+ and Mg2+ ions transfer from anode to cathode and deposit on the membrane and catalyst layers, which may cover the active catalyst sites, block the proton transport inside the membrane and degrade the catalyst ionomer layers.References Sazali N. Emerging technologies by hydrogen: A review. International Journal of Hydrogen Energy. 2020 (45): 18753-18771Becker H, Murawski J, Shinde DV, Stephens IEL, Hinds G, Smith G. Impact of impurities on water electrolysis: A review. Sustainable Energy & Fuels. 2023;7(7):1565-603.

Exploring Low Temperature Proton Exchange Membrane Water Electrolysis Anode Catalyst Degradation Under Cathode Backpressure Conditions

Hydrogen is expected to play an important role in the decarbonization of the future energy landscape by integrating renewable, nuclear, and fossil fuels and using excess power from the grid to produce H2 that can then be stored and used for a variety of applications ranging from ammonia and steel production, stationary power, buildings, and transportation.1 In order to achieve low-cost hydrogen production that is competitive with steam methane reformation (SMR), it is necessary to decrease the capital cost and this can be done by leveraging variable renewable energy (VRE) as an electricity feedstock for LTE.2 However, cost, and durability are still current challenges in state-of-the art water electrolysis systems. More research is needed to better understand the effects of dynamic operation on electrolyzer degradation. Understanding the degradation mechanisms governing intermittent electrolysis operation can enable future improvements related to component design and system operation.In recent years, electrolyzer anode degradation has been investigated during continual intermittent operation at the single cell level. Square-wave potential cycling demonstrated higher anode degradation compared to the triangle-wave cycling over the same 525 hour test (21.9 d).3 Electrolyzers operating at differential pressures and producing electrochemically compressed hydrogen could decrease the hydrogen production cost by eliminating the need for equipment related to mechanical compression.4 This work investigates the dynamics of low-temperature proton exchange membrane (PEM) electrolyzers, with a specific focus on anode catalyst layer degradation from redox transition when subjected to hydrogen crossover from cathode backpressure conditions. While cathode backpressure and operation requirements are well understood from an industry perspective, its impact on degradation mechanisms and loss rates has been relatively underexplored when low-temperature electrolysis is focused on cost reduction and variable load.In this study, hydrogen cross-over rates were varied by cathode backpressure conditions (ambient to 30 Bar) and were compared to elucidate the impact hydrogen has on anode catalyst layer degradation. The durability test duration varied from 168 – 500+ hrs. Hydrogen cross-over rates were found to correlate to cell potential during operational shutdowns and loss rates during load cycling. Electrochemical impedance spectroscopy further demonstrates higher degrees of kinetic loss and the immergence of additional loss mechanisms. The findings presented in this research contribute to the fundamental understanding of low-temperature PEM electrolysis dynamics under cathode backpressure conditions. The implications of this research offer practical insights for the design and operation of efficient and durable electrolysis systems crucial for the advancement of sustainable hydrogen production technologies.(1) H2@Scale. Hydrogen and Fuel Cell Technologies Office. https://www.energy.gov/eere/fuelcells/h2scale.(2) Mark, R.; Jadun, P.; Gilroy, N.; Connelly, E.; Boardman, R.; Simon, A. J.; Elgowainy, A.; Zuboy, J. The Technical and Economic Potential of the H2@Scale Concept within the United States; NREL/TP-6A20-77610; National Renewable Energy Laboratory: Golden, CO, 2020.(3) Alia, S. M.; Reeves, K. S.; Yu, H.; Park, J.; Kariuki, N.; Kropf, A. J.; Myers, D. J.; Cullen, D. A. Electrolyzer Performance Loss from Accelerated Stress Tests and Corresponding Changes to Catalyst Layers and Interfaces. Journal of The Electrochemical Society 2022, 169 (5), 054517. https://doi.org/10.1149/1945-7111/ac697e.(4) Ragnhild Hancke, Thomas Holm, and Øystein Ulleberg, “The Case for High-Pressure PEM Water Electrolysis,” Energy Conversion and Management 261 (2022): 115642, https://doi.org/10.1016/j.enconman.2022.115642. Figure 1

Operando Stress Evolution in Hard Carbon Anodes – Insight into the Mechanical Degradation Induced Failure Mode in Rechargeable Sodium Ion Batteries

Microstructural instabilities in electrodes arising from cycling induced stress is a primary failure mode in rechargeable batteries. Therefore, a quantitative knowledge of the cycling induced stress evolution in rechargeable battery electrodes is important for understanding the electrode microstructural instabilities during cycling that can potentially inform the electrode design to prolong battery cycle life. The cycling induced stress in electrodes typically arises from the volume changes associated with insertion/extraction of the electroactive species in the electrode matrix. For example, operando measurement of lithiation-delithiation induced stress in graphite electrodes that typically show 10% volume change has previously resulted in useful information that correlates well with the lithiation-delithiation mechanism in graphite anodes1. The size of the shuttling-electroactive species can be taken as an indicator of the cycling induced stress magnitude that drives the electrode microstructural instabilities. In this regard, quantification of the cycling induced stress in rechargeable Na-ion battery electrodes is warranted for understanding mechanical degradation induced failure modes owing to the larger size of the electroactive species, i.e., Na ions (vs. Li-ion).Hard carbons as potential anodes in rechargeable sodium ion batteries has gained considerable attention in the recent past due to their superior Na-ion storage capability (vs. graphite that is a canonical anode in rechargeable lithium-ion batteries). However, hard carbon anodes typically show significant capacity fade that can potentially arise from cycling induced mechanical degradation of the anodes. Operando stress measurements coupled with comprehensive electrode microstructural characterization will provide valuable insights in this context. Here we report on the operando stress evolution in hard carbon anodes in rechargeable sodium ion batteries as probed by Multiple Optical-beam Sensing (MOS) technique that basically involves monitoring the spacings among a group of laser spot (Fig. 1). Preliminary measurements have shown that the stress correlates with the potential with a maximum around 12 MPa in compression during sodiation and tensile stress of ~ 2MPa during desodiation. Operando stress measurements are performed in hard carbon anodes in two different electrode configurations – typical composite anodes (with binder and conductive agents) and hard carbon thin film anodes (without binder and conductive agents). The thin film configuration is considered to evaluate intrinsic stress response in hard carbon anodes in absence of any secondary phase. A comparison of operando stress response in these two types of hard carbon anodes along with comprehensive electrode microstructural characterization will be presented. Additionally, attempts will be made to shed light on the current debate in the mechanism of sodium storage in hard carbon anodes by comparing operando stress response of hard carbons from multiple sources along with their structural characterization (Raman, XPS, surface area etc.). V. A. Sethuraman, N. Van Winkle, D. P. Abraham, A. F. Bower, and P. R. Guduru, Journal of Power Sources, 206, 334–342 (2012). Figure 1

Organic Trimer Molecule Electrode as a High-Performance Next-Generation Supercapacitor Material

As greenhouse gas emissions such as CO2 continue to increase on a global scale, countries around the world are making changes to reduce their net emissions. One of the primary actions being taken is attempting to decarbonize the transportation sector by moving away from fossil fuel-powered vehicles and adopting electric vehicles (EVs). Supercapacitors are electrical energy storage devices similar in concept to batteries, however they achieve a higher power output, faster charge and discharge rates, and greater longevity. These properties make them excellent devices to work in tandem with batteries that advance their collective performance capabilities in EVs. Supercapacitors using inorganic materials such as transition metal oxides have been explored extensively and although there have been advancements in the field, they continue to struggle with limitations such as mechanical degradation during cycling, low conductivity which slows the charging-discharging processes, and the utilization of environmentally toxic metals. On the other hand, quinones are a class of organic materials considered as the most promising candidates for organic electrodes due to their ≥ 2 reversible redox-active carbonyl groups, inexpensiveness, ease of structural modifications, and environmental sustainability. However, like many organic materials, they suffer from low electrical conductivity and dissolution in electrolyte. To minimize dissolution while retaining and improving its advantages, polymerizing quinones has become a popular modification alternative, especially via polyimide and polythioether bonds. However, because polymer chains are so large and inherently have low electronic conductivity, polymerizing quinones inhibits charge transfer throughout a matrix with a carbon substrate (i.e., rGO, CNT, carbon black) due to interference with the conductive network.In this research, a smaller molecule was made from covalently bonding two different quinones via imide bonds to make an organic trimer. This helped reduce dissolution in electrolyte compared to its monomeric components via increasing the molecular weight while also improving the energy storage capabilities as a supercapacitor electrode. This is attributed to this molecule retaining the original redox active sites of its monomers and its conjugated network which allows it to achieve a 6-electron transfer mechanism per molecule. Its smaller size compared to a polymer is also hypothesized to reduce the degree of conductivity interruptions it causes when part of a carbon substrate network. While polymer chains can agglomerate easily, decreasing its available specific surface area, this trimer may be more available to participate in Faradaic processes. This research hereby reports an electrode material with very high capacitance (318 Fg-1 at 5 mVs-1) and good cycling stability utilizing a low-cost carbon black substrate for supercapacitor applications to improve the performance of next-generation EVs.

Effect of Lithiation and Delithiation on the Mechanical Properties of Electrodeposited LiCoO2 Cathode

Mechanical degradation of cathode active material, such as cracks result from volume changes and phase transitions, is one of the main causes of capacity fading in lithium-ion batteries. Understanding the active material’s deformation behavior during cycling and the impact of electrochemical charging on mechanical properties is crucial for understanding the mechanical degradation mechanism and extending battery lifetime.Herein, we investigate the mechanical properties of an electroplated LiCoO2 (LCO) cathode with crystallographic texture as a function of state of charge/discharge. Nanoindentation mapping is used to detect the differences in mechanical behavior between grain boundary and grain interior region. To determine the charged LCO crystals’ mechanical properties and avoid the effects from grain boundaries and air-exposure, in-situ nanoindentation experiments are conducted in a custom mechanical testing system within a scanning electron microscope. Considering the anisotropy of LCO, electron backscatter diffraction analysis is utilized to clarify the crystallographic orientation of the electrodeposited LCO cathode. Our result shows a decreasing tendency in elastic modulus and hardness with state of charge, which can be attributed to the expansion of LCO layered structure. The recovery of mechanical properties after discharge indicates that the changes in measured mechanical properties mainly come from Li deintercalation and intercalation rather than intergranular fracture during cycling. By releasing the relationship between mechanical properties and degree of delithiation, our study provides an insight into modeling studies of electro-chemo-mechanics for electrode materials. Figure 1

Impact of Pretension and Cycling Window on Degradation of Graphite/Silicon Composite Anodes

Challenges such as mechanical degradation and limited cycle life persist for high energy density lithium-ion batteries with silicon/graphite composite anodes. In this research work, the patterns of degradation of cells with silicon/graphite composite and NMC622 cathode are examined at varied cycling conditions and applied external pressure or pretension. The most notable outcome of this analysis is that cells cycled between 0 and 100 State-of-Charge (SoC) exhibit the most accelerated aging process. Increasing the pretension force effectively restrains the irreversible expansion of the cells, and has a positive effect on capacity retention.In this research, a comprehensive experiment was conducted involving 46 cells subjected to diverse cycling conditions, voltage windows, pretension forces, and temperatures. Reference performance tests (e.g. HPPC and 1/20 C-rate charge tests) are conducted regularly for analysis of degradation mechanisms. The capacity fade, resistance growth, and thickness increase are correspondingly shown in Figures 1, 2, and 3 with ampere hour throughput as the x-axis. The legend columns indicate test conditions, including C-rate, SoC window during cycling, temperature (in degrees Celsius), and pretension force (in psi). As is shown in all figures, there is a substantial dependence on the SoC window for cycling. To be specific, a rapid rate of capacity loss, resistance increase, and thickness increase occurs in the cell group cycled over the full SoC window (plotted in blue). Cells cycled under full SoC windows also exhibit an early accelerated fading (knee [1]) of capacity and accelerated increase (elbows [2]) of resistance and thickness. According to [3], this accelerated aging could be a consequence of side reactions and increased mechanical stress within the silicon particle when operating across a broad potential range.Meanwhile, for the cell group with restrained cycle windows (plotted in gray) the cells have not yet reached any knee, and have a relatively linear capacity loss. It should be noted that, within the range of partial cycling windows examined, cells subjected to a cycling range of 50-100 exhibit the most rapid degradation, which aligns with the conclusions presented in [4] due to the time at elevated potential. In Figure 2, the elevated temperature (depicted in red) exhibits a significant influence on the increase in resistance, potentially attributed to the growth of the solid electrolyte interface (SEI), but minimal impact on capacity loss. Maintaining other conditions constant and comparing cells under 25 psi and 15 psi (marked with hollow circles and filled circles, respectively), it is evident that a higher pretension force has a positive effect on cell capacity loss. Simultaneously, in Figure 3, the pretension force at 25 psi (marked with hollow circles) effectively restrains the irreversible expansion of the cells. The results are similar to the degradation pattern outlined in [5], it is observed that employing a high pretension force facilitates the mitigation of both degradation and expansion. As highlighted in [6], heightened temperatures lead to accelerated resistance growth. Nevertheless, the impact of various C-rates on degradation remains inconclusive [6].This research systematically analyzed cell-level degradation through an extensive array of experiments, providing valuable insights into the intricate dynamics of capacity fade, resistance increase, and thickness growth. The study's revelation that the cycle window exerts a pronounced impact on battery health could offer crucial guidance for the design of Battery Management Systems (BMS). Moreover, the work establishes a foundational basis for future research, particularly in exploring electrode-level degradation patterns. These contributions collectively enhance the understanding of energy storage systems, offering practical implications for optimizing battery performance and longevity in various applications.[1]Attia, Peter M., et al. "“Knees” in lithium-ion battery aging trajectories." Journal of The Electrochemical Society 169.6 (2022): 060517.[2] Strange, Calum, et al. "Elbows of internal resistance rise curves in Li-ion cells." Energies 14.4 (2021): 1206.[3] Verbrugge, Mark, et al. "Fabrication and characterization of lithium-silicon thick-film electrodes for high-energy-density batteries." Journal of The Electrochemical Society 164.2 (2016): A156.[4] Xu, Bolun, et al. "Modeling of lithium-ion battery degradation for cell life assessment." IEEE Transactions on Smart Grid 9.2 (2016): 1131-1140.[5] Mohtat, Peyman, et al. "Reversible and irreversible expansion of lithium-ion batteries under a wide range of stress factors." Journal of The Electrochemical Society 168.10 (2021): 100520.[6] Pannala, Sravan, et al. "An Experimental Correlation of Degradation with Cell Reversible and Irreversible Expansion Measurement in Pouch Cells." Electrochemical Society Meeting s 243. No. 2. The Electrochemical Society, Inc., 2023. Figure 1

Substitution of a Microstructure-Simulation with a Data-Driven Approach for Modelling Mechanical Degradation of Electrodes

One significant aspect of battery aging involves the mechanical degradation of battery electrodes. The intercalation of ions into the active material particles of a lithium-ion battery creates a concentration profile along the radial direction of the active material particle, influenced by transport properties and kinetics. Mechanical stresses arise due to the spatial constraints of intercalated ions, leading to the mechanical degradation of the electrode.Common cathode materials used in practical applications, such as Lithium Nickel Manganese Cobalt Oxide (NMC) or Lithium Iron Phosphate (LFP), undergo a transition from a lithium-poor phase to a lithium-rich phase during the intercalation process. Along this phase boundary, high mechanical stresses occur due to the inconsistency of the concentration profile, resulting in particle fractures. This can lead to electrical isolation and, consequently, the electrochemical inertization of the active particle material, manifested as a reduced battery capacity on a macroscopic scale.Simulating these processes poses computational challenges. Given current computational power, accurately simulating a sufficient number of cycles for a microstructure simulation, which describes transport processes within a battery, is computationally prohibitive. Therefore, this study employs data-driven models. To predict radial concentration profiles within the particle, a physics-informed neural network (PINN) proves useful by extending the cost function with the transport equation. Classical neural networks (ANN) are utilized to calculate the electrical voltage of active material particles. These models are trained with results from microstructure simulations to develop a grey-box model, enabling the inclusion of mechanical degradation in the electrode simulation.Mechanical stresses and degradations are thus investigated under various galvanostatic discharge rates to define an aging-resistant operational window for the battery.

Determination of Electrochemically Active Surface Area in All-Solid-State Batteries

All-solid-state batteries (ASSBs) are currently receiving much attention as one of the most promising next-generation rechargeable battery systems due to their promise of high energy density and high safety. Despite many efforts to commercialize ASSBs, however, there are still many unresolved technical challenges. Unlike conventional lithium-ion batteries (LIBs), the interface between the cathode and electrolyte in ASSBs exhibits a complex degradation pattern that combines chemical and mechanical degradations. In particular, the high Ni content cathode materials in ASSBs are commonly known to suffer from significant additional degradation mechanism, e.g., volume expansion/contraction due to H2-H3 phase transitions at high voltages, resulting in particle cracking. This degradation of the integrity of the active material leads to a reduction in electrochemically active surface area (active area afterward) due to loss of contact between the active material and solid electrolyte, slow diffusion rate of lithium in the active material, and isolation of the active material. These issues are recognized as major contributors to cell performance degradation. Among these issues, the changes in the active area have a decisive impact on the rate of redox reactions that are key to battery charging and discharging kinetics, so accurate determination of the active area is crucial for the diagnosis and improvement of batteries. In the electrochemical analysis of ASSBs, the poor contact between the solid electrolyte and the active material, or the change of the contact properties during the battery operation, should be a very important consideration. Especially when determining kinetic factors such as charge transfer resistance and chemical diffusion coefficient of cathode material by electrochemical methods, the models we usually use include the electrode surface area value as an important variable, so the accurate estimation of the active area is indispensable for obtaining reliable electrochemical properties. Unlike typical LIBs, in ASSBs the active material/electrolyte interface contact properties change relatively significantly during repeated cycling, so devising a reliable technique to analyze the active area of active materials in ASSBs is very crucial for the research and development of ASSBs. However, to the best of our knowledge, there are still very few studies on this.In this study, we propose promising methods to measure the contact characteristics between the cathode material and the solid electrolyte in ASSBs, namely the electrochemically active surface area, and discuss their reliability based on intercomparison and literature reports. For this purpose, first, the method for determining the active area of active materials based on galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) reported in conventional LIBs was reviewed. Then, its applicability to ASSBs was explored, and a way to improve the reliability of the analysis was proposed. Specifically, a three-electrode cathode half-cell experiment was conducted to analyze the active area of the Ni-rich cathode. The active area was calculated by comparing the diffusion coefficient measured by EIS with that obtained by GITT. When comparing the active area determined at different voltages, it was observed that the active area varies significantly with voltage most likely due to the volume change caused by the H2-H3 phase transition. The second electrochemical method performed for the determination of the active area of the active material is based on the quantification of the lithium intercalation sites on the cathode surface based on the analysis of the frequency factor in Arrhenius expression. For this purpose, battery at different charge states were kept at high temperatures for long periods of time to induce interfacial degradation. The temperature-dependent charge transfer resistance was then determined by EIS analysis, which was used to interpret the redox (or lithium absorption/desorption) reactions kinetically. The experimental results showed that the redox reaction rate followed exactly the Arrhenius relationship for all the charge states used, but the activation energies and frequency factors changed differently depending on the charge state. In this study, we discuss these results in relation to various phenomena that may occur during high-temperature aging, such as the formation of rock salt structures and cracks on the nickel-rich cathode surface, and try to estimate the change in active area. In this study, the electrochemical analysis methods of the contact characteristics between the cathode and the solid electrolyte in ASSBs will be examined in depth and their reliability will be assessed. In addition, further improvements in active area analysis techniques for active materials in ASSBs will be discussed.

(Invited) Nano-Characterization of the Internal Morphology of Polymer Electrolyte Membranes with Cryogenic Scanning Transmission Electron Microscopy

Polymer membranes play important roles in electrochemical devices such as polymer electrolyte fuel cells. In recent years, there has been a growing interest in alkaline anion exchange membrane (AAEM) fuel cells as the alkaline environment offers a potential low-cost alternative to commercial proton exchange membrane (PEM) fuel cells [1]. Nonetheless, optimization of polymer properties such as ion conductivity and mechanical durability is still necessary to achieve commercially viable AAEM based fuel cells. Often, semicrystalline polymer backbones are selected for AAEM design, aiming to replicate the exceptional performance of Nafion in PEM fuel cells where the crystalline domains are believed to act as cross-linkers, mitigating excessive water uptake and mechanical degradation [2,3].Characterizing the local polymer morphology at the nanoscale is a crucial step in understanding how to optimize the design of AAEMs with enhanced durability and ion conductivity. Imaging polymers using conventional transmission electron microscopy (TEM) techniques is challenging however, due to their inherently-high beam sensitivity and low image contrast. Here, we demonstrate nanometer-resolution mapping of the ordering in polymer electrolyte membranes using cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM). Conventionally used for mapping inorganic crystalline materials, the 4D-STEM technique has more recently also found applications in mapping semicrystalline, soft materials as well [4,5]. Here, using a model system of semicrystalline hydrogenated polynorbornene (hPN) AAEMs [6], we demonstrate the effects of polymer synthesis including molecular weight and thermal history on crystalline morphology and in turn on the polymer performance. Further, we compare the crystalline architecture of the hPN copolymers to that of Nafion 212 (Figure 1). Our results suggest that polymers with homogeneously distributed, nanometer-size crystalline domains lead to improved water management, a property directly related to the mechanical integrity of the polymer, with possible impacts on ion conductivity. More broadly, the results give new insights into how we can tune AAEM design in order to improve their performance.[1] Dekel, Journal of Power Sources, 375, 158-169. (2018).[2] Yang, et al. Chemical Reviews, 122(6), 6117-6321. (2022).[3] Mauritz & Moore, Chemical reviews, 104(10), 4535-4586. (2004).[4] Panova, et al. Nature materials, 18(8), 860-865. (2019).[5] Bustillo, et al. Accounts of chemical research, 54(11), 2543-2551. (2021).[6] Treichel, et al. Macromolecules, 53(19), 8509-8518. (2020).Figure 1: Cryo-4D-STEM crystallinity maps of hPN-co-iPrMe copolymers with varying syntheses and Nafion 212. We observe improvement in the water management of the copolymer membranes as the crystalline domains are reduced in volume and distributed homogeneously. The chemical structures of the polymers are listed below the crystallinity maps. Figure 1

Research and Development Needs to Enable Renewable-Powered Liquid Alkaline Electrolyzers

Low temperature electrolysis (LTE) is the most promising method for fully renewable hydrogen production. However, to compete with current hydrogen production methods (which produce CO2), substantial cost reductions and efficiency improvements are necessary. Of the various LTE technologies, liquid alkaline (LA) electrolysis is the most mature. It has proven large scalability and can operate with all earth-abundant materials. However, most conventional LA electrolyzers are limited to lower current density operation than newer LTE technologies.Most LA electrolyzers operate with uncatalyzed Ni anodes, despite the existence of many highly active catalysts for oxygen evolution in alkaline conditions. This is because catalyzed systems require constant operation, as the catalyst layers degrade and delaminate rapidly upon exposure to the reverse polarization conditions experienced during system shutdown. This limitation prevents the integration of catalyzed electrodes, as even a single unexpected plant shutdown causes significant efficiency and cost losses. Further, this prevents fully catalyzed LA electrolyzers from directly operating with renewable power sources with large power fluctuations. Therefore, the development of reverse-current tolerant catalyst layers is essential to enable high-efficiency renewable energy powered LA electrolyzers.This talk will detail the mechanisms of electrode degradation during electrolyzer system shutdown. Our findings reveal anode catalyst layers fail through a combined electrochemical and mechanical degradation mechanism. I will discuss key differences in the cathode versus anode operating environments that explain the difference in reverse current tolerance. Considering these results, I will highlight priority research and development directions for developing anode and cathode catalysts for renewable-powered LA electrolyzers.

Water-rock interfacial softening model of cemented soft rock: An experimental and numerical study

Cemented soft rock is prone to softening when exposed to water, and its mechanical properties deteriorate rapidly, which is an important reason to induce the instability and failure of engineering soft rock mass. The softening mechanism of soft rock is essentially the deterioration of microstructure caused by the change of water-rock interface. Considering the general characteristics of soft rock, the microstructural evolution characteristics and element loss over varying immersion time are then compared and analyzed. The Interfacial Cemented Bonding (ICB) structure is proposed to describe the evolution of water-rock interface. Based on the diffusion theory, the theoretical equation describing the evolution of water-rock interface is derived and compared with the experimental results. The meso-softening damage factor (MSDF) of soft rock is proposed and introduced into a numerical method to establish a strength degradation discrete element method (SD-DEM) model. The results show that the softening process of soft rock is accompanied by the shedding and suspension of particles and the dissolution of soluble substances. Besides, the softening of soft rock has obvious nonlinear dynamic characteristics. The fitting degree between the theoretical values and the experimental results is relatively high, which verifies the reliability and rationality of the dissolution-diffusion interfacial softening model. The numerical results are in good agreement with the experimental ones. This study provides a new idea for understanding the mechanism of water-induced softening characteristics and strength degradation of soft rock.

Coupling Electro-Fenton and Electrocoagulation of Aluminum-Air Batteries for Enhanced Tetracycline Degradation: Improving Hydrogen Peroxide and Power Generation.

Electro-Fenton (EF) technology has shown great potential in environmental remediation. However, developing efficient heterogeneous EF catalysts and understanding the relevant reaction mechanisms for pollutant degradation remain challenging. We propose a new system that combines aluminum-air battery electrocoagulation (EC) with EF. The system utilizes dual electron reduction of O2 to generate H2O2 in situ on the air cathodes of aluminum-air batteries and the formation of primary cells to produce electricity. Tetracycline (TC) is degraded by ·OH produced by the Fenton reaction. Under optimal conditions, the system exhibits excellent TC degradation efficiency and higher H2O2 production. The TC removal rate by the reaction system using a graphite cathode reached nearly 100% within 4 h, whereas the H2O2 yield reached 127.07 mg/L within 24 h. The experimental results show that the novel EF and EC composite system of aluminum-air batteries, through the electroflocculation mechanism and ·OH and EF reactions, with EC as the main factor, generates multiple •OH radicals that interact to efficiently remove TC. This work provides novel and important insights into EF technology, as well as new strategies for TC removal.

(Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation) Science of Multiphysics Behavior of Si/C Composite Anodes in High-Energy-Density Lithium-Ion Batteries

The rapidly growing demands on energy storage technologies over the last decade have imposed further requirements for the high energy/power density, safety, and durability of lithium-ion batteries (LIBs). Si/C composite materials have attracted enormous research interest as the most promising candidates for the anodes of next-generation lithium-ion batteries, owing to their high energy density and mechanical buffering property. However, the major disadvantage of materials with ultra-high capacities, such as Si-based materials, is the significant volume change during cycling, which further leads to mechanical and electrochemical degradation. However, a sophisticated and quantitative understanding of the highly electrochemical-mechanical coupling behaviors is still lacking.A comprehensive computational model is indispensable in the developing process of the excellent performance of anode material due to the low-realizability, inconvenience, and high-cost of experiments, which also provides powerful tools for fabrication guidance of novel Si/C composites designs. Hence, a multiphysics modeling framework is established with a detailed geometric description to quantitatively reveal the underlying governing mechanisms of Si/C composite anode behaviors. We studied the effects of the Si weight percentage, the Si-related particle distribution, the Si-related particle size, the mechanical constraint, and the binder domain gradient on the battery performance regarding the potential behavior, capacity delivery, mechanical stress/strain, Li plating, and polarization evolution. In our study, we used silicon monoxide (SiO) as the Si element source and graphite (Gr) as the C element source. Results discover that an 8-10 wt% of SiO would be an optimal choice regarding capacity delivery and minimizing Li plating under 1C constant current charging condition. Positioning SiO particles near the separator and reducing the sizes of SiO particles are also demonstrated to be beneficial for electrochemical performance with trivial influence on mechanical mismatch. In addition, the mechanical constraint demonstrates a balanced effect on the overall performance of cells and the local behaviors of particles. Our findings also indicate that reducing the proportion of carbon-binder domain (CBD) in the upper domain (near the anode surface) compared to the lower domain (near the current collector) positively influences electrochemical performance, particularly in terms of capacity and Li plating. However, such an arrangement introduces potential risks of mechanical failures and we recommend to incorporate a higher proportion of CBD alongside the SiO particles. Finally, an anode design with a lower CBD proportion in the upper domain exhibits superior rate performance.This study explores the multiphysics behavior of Si/C anodes material using a comprehensive methodology combining experimental and FEA techniques, systematically revealing the coupling mechanism among various physical fields, as well as providing efficient and powerful tools in the design, development, and evaluation of high energy density lithium-ion batteries.