High-Energy Lateral Mapping (HELM) Studies of Inhomogeneity and Failure Mechanisms in NMC622/Li Pouch Cells
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99 GENERAL AND MISCELLANEOUS↗
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Valuation of Surface Coatings in High-Energy Density Lithium-ion Battery Cathode Materials
Artificial barriers, usually with either electrochemically active or inactive coating materials, are deployed on cathode material surfaces to mitigate detrimental side reactions by suppressing direct contact of cathode and electrolyte called surface coatings. These surface coatings are commonly known to increase the wettability of liquid electrolyte and reduce the interfacial charge transfer resistance. An important caveat is the selection of appropriate coating material with appropriate thickness for achieving enhanced electrochemical performance. As modern battery materials are increasingly developed with some type of surface coating, a careful and thorough examination of their role in mitigating the cycle life issues of cathode materials is paramount. Here, this comprehensive review article extensively covers the selection criteria of coating materials based on their chemical and physical properties and electrochemical functionalities. Additionally, the article discusses the concept of critical coating thickness and methods of achieving homogeneous coating architectures that deliver desired performance benefits. Furthermore, this comprehensive article summarizes the recent advancements, effectiveness, necessity of cathode surface coatings and identifies the key aspect of structure-property correlation between coating type/thickness and lithium-ion diffusion through coating layers as the linchpin that validates surface coating approaches especially for high capacity nickel-rich cathodes.
25 ENERGY STORAGE↗
Manufacturing Cathodes via Dry-Processing for Lithium-Ion Batteries
Conventional lithium-ion battery (LIB) electrodes are prepared through a wet slurry process with n-methyl pyrrolidone solvent, especially for cathodes. The wet slurry process encounters several disadvantages such as binder migration, electrode cracking in thick electrodes, energy intense heat-dry NMP solvent removal, and costly NMP recovery. The cost and energy consumption of coating and drying of electrode are about 11.5 % and > 46 % in LIB manufacturing, respectively. Thereby, it is essential to develop a facile roll-to-roll solvent-free LIB electrode processing for reducing the cost and energy consumption. Recently, the Maxwell-type dry processing (DP) shines new lights on LIB manufacturing, which mainly bases on dry mixing (DM) of electrode component powder followed by calendering into electrode films and laminating onto current collectors, realizing the rapid manufacturing of LIB electrodes in a powder-to-film manner for industries. This report shares some recent progress on the DP from our group. We aim to further advance the manufacturing science of DP by correlating the processing conditions with electrode properties and performance. Particularly, we investigate the effect of DM, and compression on the polytetrafluoroethylene (PTFE) binder fiberization, porosity, mechanical properties, electrical conductivity and electrochemical behaviors of electrodes. The DM study suggests that PTFE fiberization heavily relies on the degree of DM. Insufficient DM results in poor PTFE fiberization while outrageous DM damages the formed PTFE fibers. Both negatively affect the mechanical behaviors of the electrodes and their rate capability. However, moderate DM is highly beneficial. In addition, our study of the porosity impact reveals that LiNi0.8Mn0.1Co0.1O2 (NMC) secondary particles can be broken into primary particles due to compression, especially at low porosity. Those fractured NMC secondary particles exhibit lower modulus. We propose that a moderate porosity of around 32% favors the electronic conductivity, charge transfer impedance and rate capability. The study of the cathodic electrolyte interphase layer of PTFE-based DPed electrode confirms that side reactions of PTFE binder due to the formation of LiF in LiClO4-based electrolyte.
Tao, Runming↗
Understanding Operando Water Management in Hydroxide‐Exchange‐Membrane Fuel Cells
The water balance in hydroxide-exchange-membrane fuel cells (HEMFCs) is a key challenge for improved performance and durability, intimately linked with the various interfaces and coupled phenomena. For every 4 electrons produced, 4 water molecules are generated in the anode and 2 consumed in the cathode, while electroosmosis transports water across the HEM from the cathode to the anode. Consequently, a concentration gradient drives water back, from anode to cathode. Ineffective water management could lead to cathode dry-out, limiting reaction rate and causing ionomer degradation, or to anode flooding. To address these concerns, it is critical to measure the water transport operando . Herein, a home-built water-flux station is used to measure total water flux during cell operation with different inlet relative humidities and back pressures. Increasing the HEM thickness fourfold decreases the water flux at high current density, and utilizing microporous layers on both the anode and cathode decreases the water flux from the anode to the cathode. However, the most significant variable in changing the water flux was found by increasing the anode back pressure. Furthermore, humidity cycling significantly changed electrochemical performance without affecting the overall water fluxes. These findings can be translated to other devices utilizing an HEM.
AEMFC↗
Non-planar platinum group metal-free fuel cell cathodes for enhanced oxygen transport and water rejection
Proton exchange membrane fuel cells (PEMFC) with cathodes using platinum group metal-free (PGM-free) catalysts could significantly reduce costs, but the lower volumetric oxygen reduction reaction (ORR) activity requires thick electrodes that suffer from liquid water flooding and increased oxygen transport resistance. To address these challenges, we developed a 3D gas diffusion electrode (GDE) architecture to enhance liquid water removal through the diffusion media and reduce cathode saturation. The cathode features a uniform catalyst layer adjacent to the membrane for high ORR activity and then pillars of the hydrophilic catalyst layer that pass through the microporous layer (MPL), providing a low capillary pressure barrier pathway to the carbon fiber paper layer and channel. The non-planar cathode also increases the interfacial area between the catalyst layer and hydrophobic MPL for a greater fraction of the cathode with high O 2 concentration. Our studies included parametric experimental study of the pillar density to identify the optimum pitch between pillars. Our measurements show significant improvements in the mass transport region of the polarization curve with 3D structured electrodes leading to an 8% increase in maximum current density, 19% increase in maximum power density, and 16% increase in current density at 0.67 V with air.
25 ENERGY STORAGE↗
Performance of 30-cm ion thrusters with dished accelerator grids
Thirteen sets of dished accelerator grids were treated on five different 30 cm diameter bombardment thrusters to evaluate the effects of grid geometry variations on thruster discharge chamber performance. The dished grid parameters varied were: grid-to-grid spacing, screen and accelerator grid hole diameter, screen and accelerator open area fraction, compensation for beam divergence losses, and accelerator grid thickness. The effects on discharge chamber performance of main magnetic field changes, magnetic baffle current, cathode pole piece length and cathode position were also investigated.
Rawlin, V. K.↗
Surface heterogeneity propagation and homogenization for pouch cell-scale Li metal anodes
Li metal anode is a promising candidate for next-generation energy storage systems and is widely explored in Li-ion and solid-state batteries. Despite its potential, Li metal anodes face instabilities during long-term cycling, especially when paired with NMC or sulfur-based cathodes, where Li is cycled at high capacities of 6-8 mAh/cm2, equivalent to a thickness of 30-40 µm. During such extensive utilization, degradation mechanisms such as excessive solid electrolyte interphase (SEI), dendrites, and dead Li emerge, and ultimately lead to sudden failure and reduced cycle life. The origin of the degradation mechanisms stem from surface heterogeneities introduced during Li foil manufacturing and storage [1, 2]. As cycling progresses, the local heterogeneities propagate, resulting in uneven Li utilization and degradation-prone regions across the electrode [3], which consequently induce performance variations at the cell level. This heterogeneity propagation is particularly pronounced in large-format pouch cells in practical applications, where the surface effects are magnified. Without a clear understanding of the multi-scale heterogeneities and the development of surface homogenization methods, the performance consistency will be compromised, hindering the commercialization of Li metal batteries. In this presentation, we investigate the evolution of surface heterogeneity propagation on commercially available Li foils. We discover that inhomogeneous Li utilization appears as early as the first half-cycle of formation, manifesting as localized clusters and pits. In pouch cell configurations, these features exhibit areal density variations across the electrode on a scale of millimeters. To improve Li utilization homogeneity, a scalable mechanical brushing method is introduced to remove the chemically heterogeneous surface passivation layer. Furtherore, the influence of utilization homogeneity on cell-to-cell consistency is evaluated using 32 Li-NMC811 pouch cells divided into as-received and brushed Li groups. On the brushed Li, clusters and pits are no longer observable, and the cells exhibit significantly improved consistency in discharge capacity trajectories and cycle lifetime. Overall, this study highlights the role of Li surface utilization homogeneity on long-term cycling performance. Our research provides a pathway for improving large-area electrode uniformity and establishing evaluation methods for cell-to-cell consistency, both are key steps toward the commercialization of Li metal batteries and beyond. [1] Otto, Svenja-K., et al. "In-depth characterization of lithium-metal surfaces with XPS and ToF-SIMS: toward better understanding of the passivation layer." Chemistry of Materials 33.3 (2021): 859-867. [2] Hatzell, Kelsey, et al. "Aligning lithium metal battery research and development across academia and industry." Joule (2024). [3] Kim, Sangwook, et al. "Calendar life of lithium metal batteries: Accelerated aging and failure analysis." Energy Storage Materials 65 (2024): 103147.
25 - ENERGY STORAGE↗
Multiscale Cryo Electron Microscopy Reveals Interfacial Degradation and Stabilization in Battery Electrodes
Electrochemical interfaces are dynamic systems, evolving based on their local environment and reactant surface structures. The electrode-electrolyte interface in Li-ion batteries can be protective, limiting parasitic reactions with the electrolyte to passivate the surface [1]. Additionally, this interphase has an impact on the Li-ion transport through that layer based on its composition, bonding environment, and thickness. These parameters are challenging to collect and may vary depending on the electrode surface site investigated relative to its spatial position in a coin cell. This study will detail a multiscale cryogenic electron microscopy approach where millimeter-scale cross-sections through the coin cell batteries were made using a cryogenic stage within a fs-laser plasma focused ion beam (laser PFIB) with complementary energy dispersive X-ray spectroscopy able to detect variations in the composition at electrode interfaces [2]. Microscale cross-sectioning and lamella sample preparation of battery electrodes was conducted at the Center for Integrated Nanotechnologies using a Ga-ion focused ion beam (FIB) with air-free and cryo-transfer [3], followed by nanoscale mapping of composition and bonding within the CEI through cryo-scanning transmission electron microscopy (cryo-STEM) electron energy loss spectroscopy [4]. This multiscale approach enabled identification of millimeter-scale features of a battery stack with visualization of degradation in electrodes such as cracks in cathode particles, gas evolution, and SEI evolution; microscale interfacial characteristics, such as heterogeneity in the SEI or barrier layer and identification of electrolyte networks to the electrode surfaces; and nanoscale measurement of the CEI thickness, mapping of transition metal bonding within the cathode particles to identify loss of active materials, and identification of beneficial electrolyte additives incorporated into the CEI structure. This multiscale approach allows for a statistical understanding of the primary mechanisms and parasitic degradation pathways that impact performance by limiting the ion transport pathways within Li+ batteries.
36 MATERIALS SCIENCE↗
Resolution of electron emission mechanisms in an argon arc with a hot tungsten cathode
The regenerative nature of the interaction between the electron emission processes at the cathode surface and the ion-, excited-atom-, and photon-production processes in the plasma was examined. Semiquantitative estimates of the thickness of the species production layer, the current partition, and the time constants were made. These results were used to interpret experimental measurements of the current decay of an argon arc at 46.7 kPa, 3.2-7.9 A, and 28-18 V, with a self-sustained hot tungsten cathode. After the discharge is suddenly connected to a voltage clamp, the disparity of decay rates for different emission processes permits the separation of thermionic emission from the faster-decaying components. The observed thermionic current constitutes about 30% of the total emission. The high nonthermionic portions of the current could not be explained in terms of the present understanding of the emission processes.
Chen, M. M.↗
Extreme fast charge aging: Effect of electrode loading and NMC composition on inhomogeneous degradation in graphite bulk and electrode/electrolyte interface
Empowering extreme fast charging (XFC) requires a comprehensive understanding of its application with advanced anode and cathode materials in lithium-ion batteries. No report exists for the full extent of limitations for the anode with crosstalk effect from paired cathode as well as Li plating due to electrode loading under XFC. In this study, a combination of cell testing and multiple length characterization is used to investigate XFC aging mechanism in cells with a low loading of 1.5 mAh cm -2 and high loading of 2.5 mAh cm -2 for graphite (Gr)/Ni-rich LiNi x Mn y Co 1-x-y O 2 (NMCs). Operando XRD mappings show 1.5 mAh cm -2 loadings result in higher strain in graphite for all three cathode types. Among the three NMC cathodes, the graphite from NMC532 and NMC811 cells show comparable strain. Scanning electron microscopy (SEM) images show distinct differences between 6-C-charged anodes in two loadings. Significantly increased electrode thickness can be seen due to more damage in the graphite bulk and accumulation of the electrolyte decomposition products in electrode pores. X-ray photoelectron spectroscopy (XPS) reveals both cathode chemistry and Li plating influence the non-uniform SEI composition on graphite surface. We report higher Ni content in NMC811 promotes the higher levels of salt decomposition on the SEI and formation of higher mass of electrolyte aging products.
25 ENERGY STORAGE↗
Electrochemistry-induced deposition for controlled formation of metal–organic framework films on insulator and conductor substrates
A number of technological applications of metal–organic frameworks (MOFs) require the formation of their thin films on insulator and/or conductor substrates at selected areas with desired thicknesses. However, fabrication of such MOF films often requires multi-step processes and/or sophisticated instruments. Herein, we discuss electrochemistry-induced MOF deposition, which permits the direct formation of a thin MOF film with controlled thickness at a desired area on various substrates. So far, we have reported the applicability of this deposition method for the formation of zeolitic imidazolate framework-8 (ZIF-8) films. In this method, a ZIF-8 film is formed on an insulator or a conductor substrate upon applying a cathodic potential to a working electrode that is placed above the substrate. Importantly, the film is formed just below the cathodic working electrode, indicating that the position and lateral dimensions (on the mm- to μm-scale) of the film can be controlled by those of the working electrode. In addition, film thickness is controllable in the range of tens to hundreds of nanometers by adjusting potential application conditions at the cathodic working electrode. These results show that the electrochemistry-induced deposition method will provide a simple means for the fabrication of a patterned MOF film on various substrates without additional lithographic processes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Quantitative assessment of environmental phenomena on maximum pit size predictions in marine environments
Maximum pit sizes were predicted for dilute and concentrated NaCl and MgCl 2 solutions as well as sea-salt brine solutions corresponding to 40% relative humidity (RH) (MgCl 2 -rich) and 76% RH (NaCl-rich) at 25 °C. A quantitative method was developed to capture the effects of various cathode evolution phenomena including precipitation and dehydration reactions. Additionally, the sensitivity of the model to input parameters was explored. Despite one's intuition, the highest chloride concentration (roughly 10.3 M Cl – ) did not produce the largest predicted pit size as the ohmic drop was more severe in concentrated MgCl 2 solutions. Therefore, the largest predicted pits were calculated for saturated NaCl (roughly 5 M Cl – ). Next, it was determined that pit size predictions are most sensitive to model input parameters for concentrated brines. However, when the effects of cathodic reactions on brine chemistry are considered, the sensitivity to input parameters is decreased. Although there was not one main input parameter that influenced pit size predictions, two main categories were identified. Under similar chloride concentrations (similar RH), the water layer thickness (WL), and pit stability product, (i · x) sf , are the most influential factors. When varying chloride concentrations (RH), changes in WL, the brine specific cathodic kinetics on the external surface (captured in the equivalent current density (i eq )), and conductivity (k o ) are the most influential parameters. Finally, it was noted that dehydration reactions coupled with precipitation in the cathode will have the largest effect on predicted pit size, and cause the most significant inhibition of corrosion damage.
54 ENVIRONMENTAL SCIENCES↗
A lightweight and metal-free current collector for battery anode applications
The requirement for high energy density batteries is driving the development of high-capacity electrode materials while reducing the amount of inactive battery components such as separators, binders, and current collectors. Though current collectors are an inactive component, they are still required for successful working of a battery cell. Conventional current collectors include aluminum foil for cathode and copper foil for anode. Copper foil is quite heavy (8.7 mg/cm 2 ) for 10μm thickness. Therefore, there is a need for a lightweight current collector for anode applications. In this work, a metal-free current collector comprised of aligned carbon fiber (CFs) layer filled with carbon nanotubes (CNTs) mixed in polymer (P) is developed to be used as a current collector for anodes. Further, anodes coated on the CF-CNT-P showed lower charge transfer resistance and improved rate capability compared with the anodes fabricated on conventional copper foil-based current collectors. The CF-CNT-P are lighter (≈1.5 mg/cm 2 ) than the commonly used copper foil (8.7 mg/cm 2 ), which will increase the gravimetric energy density.
25 ENERGY STORAGE↗
Redox-homogeneous, gel electrolyte-embedded high-mass-loading cathodes for high-energy lithium metal batteries
Lithium metal batteries have higher theoretical energy than their Li-ion counterparts, where graphite is used at the anode. However, one of the main stumbling blocks in developing practical Li metal batteries is the lack of cathodes with high-mass-loading capable of delivering highly reversible redox reactions. To overcome this issue, here we report an electrode structure that incorporates a UV-cured non-aqueous gel electrolyte and a cathode where the LiNi 0.8 Co 0.1 Mn 0.1 O 2 active material is contained in an electron-conductive matrix produced via simultaneous electrospinning and electrospraying. This peculiar structure prevents the solvent-drying-triggered non-uniform distribution of electrode components and shortens the time for cell aging while improving the overall redox homogeneity. Moreover, the electron-conductive matrix eliminates the use of the metal current collector. When a cathode with a mass loading of 60 mg cm -2 is coupled with a 100 µm thick Li metal electrode using additional non-aqueous fluorinated electrolyte solution in lab-scale pouch cell configuration, a specific energy and energy density of 321 Wh kg -1 and 772 Wh L -1 (based on the total mass of the cell), respectively, can be delivered in the initial cycle at 0.1 C (i.e., 1.2 mA cm -2 ) and 25 °C.
25 ENERGY STORAGE↗
Ultrahigh Areal Capacity Holey Graphene Air Cathodes for Li-O2 and Li-CO2 Batteries
Advanced lithium (Li) batteries using gaseous cathode reactants such as oxygen (O2) and carbon dioxide (CO2)are attractive energy storage platforms because the gases are obtained externally and thus not accounted for in the total battery weight when fully charged.The discharge products at the cathode, typically Li2O2 for Li-O2 batteries and Li2CO3 for Li-CO2 batteries, are insoluble in the electrolyte.Therefore, in order for such batteries to function properly, an “air cathode”,which is a conductive scaffold within the battery cell,is required as a physical location for cathode electrochemical reactions to occur. Prior research has identified many carbon nanomaterials such as carbon nanotubes and graphene as viable choices for air cathode scaffold, while various metallic and metal-free catalytic systems integrated onto carbon-based air cathodes have been developed to improve the sluggish discharge and charge reactions. For future practical applications, the air cathode must exhibit a usable capacity per unit electrode area, or areal capacity, a critical parameter that has been largely overlooked so far in this field. In order to achieve high areal capacity, the air cathode must exhibit a sufficient amount of accessible void volume per unit electrode area while maintaining the conductive scaffold integrity during the entire electrochemical process. Here we present an ultrathick,holey graphene-based air cathode platform fabricated from a facile dry compression process that exhibits remarkable areal capacity values. Holey graphene is a carbon nanomaterial derived from graphene, but with nanometer sized holes through the nanosheet thickness.The presence of these holes enhances mass transport through electrode thickness and also enables the unique dry-press fabrication process that is not achievable using other carbon scaffold materials.The dry-pressed holey graphene air cathode platform is not only compatible with catalyst incorporation to improve battery reaction kinetics, but also allows for novel engineering of electrode architectures that is not achievable using conventional electrode fabrication approaches.The applications of such highly versatile, ultrahigh areal capacity air cathode platforms to both Li-O2 and Li-CO2 battery chemistries will be discussed.
Li-O2 batteries, Li-CO2 batteries, holey graphene,↗
Stabilizing High–Nickel Cathodes with High–Voltage Electrolytes
Electrolytes connect the two electrodes in a lithium battery by providing Li + transport channels between them. Advanced electrolytes are being explored with high-nickel cathodes and the lithium-metal anode to meet the high energy density and cycle life goals, but the origin of the performance differences with different electrolytes is not fully understood. Here, the mechanisms involved in protecting the high-capacity, cobalt-free cathode LiNiO 2 with a model high-voltage electrolyte (HVE) are delineated. The kinetic barrier posed by a thick surface degradation layer with poor Li + -ion transport is found to be the major contributor to the fast capacity fade of LiNiO 2 with the conventional carbonate electrolyte. In contrast, HVE reduces the side reactions between the electrolyte and the electrodes, leading to a thinner nano-interphase layer comprised of more beneficial species. Crucially, the HVE leads to a different surface reorganization pathway involving the formation of a thinner nanoscale LiNi 2 O 4 spinel phase on the LiNiO 2 surface. Finally, with a high 3D Li + -ion and electronic conductivity, the spinel LiNi 2 O 4 reorganization nanolayer preserves fast Li + transport across the cathode–electrolyte interface, reduces reaction heterogeneity in the electrode and alleviates intergranular cracking within secondary particles, resulting in superior long-term cycle life.
25 ENERGY STORAGE↗
Magnetized, radiofrequency-driven hollow cathode chemical-vapor deposition of ultrathick hydrogenated amorphous carbon
Amorphous carbon is an attractive material for next-generation inertial confinement fusion (ICF) ablators due to its amorphous structure, tunable density, compatibility with dopants, chemical inertness, and mechanical robustness. Ablators are typically deposited as ultrathick (10–200 μm) coatings on removable spherical templates. The deposition of such thick amorphous carbon films is challenging due to high intrinsic compressive stress, which causes film buckling and delamination. Here, we study the deposition of amorphous carbon films by magnetized, radiofrequency-driven hollow cathode chemical vapor deposition with a custom-designed source in Ne plasmas. Emphasis is on the hollow-cathode source design and effects of the plasma discharge power and the precursor flow rate on film properties. We demonstrate deposition rates of >1 μm/h for films with hydrogen content of ∼40 at. %, densities of 1.1–1.7 g/cm 3 , and trace quantities of oxygen impurities. In conclusion, we also demonstrate the feasibility of depositing thick hydrogenated amorphous carbon films (∼30 μm) for ICF applications.
Carbon based materials↗
4D-STEM Coupled with Unsupervised Machine Learning to Reveal at Large-Scale the Microstructural Evolution in Li- and Mn-Rich Cathodes
Li- and Mn-rich (LMR) layered oxides are known to exhibit a thin surface reconstruction layer, which grows during electrochemical cycling in a manner that depends on exposed crystallographic facets, cycling conditions, and electrolyte chemistry. Direct characterization of this layer has traditionally relied on high-resolution electron microscopy, which is inherently limited to small fields of view. Here, we employ four-dimensional scanning transmission electron microscopy (4D-STEM) combined with unsupervised machine-learning clustering to quantitatively map phase distributions over large areas and track their evolution in LMR cathodes during electrochemical aging. Our results show that the surface reconstruction layer consists predominantly of a rocksalt phase, whose thickness varies across different facets following activation cycling and becomes substantially thicker and more uniform during calendar aging. In contrast, a spinel-like phase is observed within the particle bulk. Large-area phase mapping and correlative high-resolution imaging reveal that this spinel-like phase preferentially nucleates at bulk crystallographic defects, including boundaries between 60°-rotated layered domains and associated mixed-phase regions, rather than exclusively at the particle surface. Our findings establish a mechanistic distinction between surface-driven rocksalt formation and bulk-defect-mediated spinel nucleation while demonstrating the unique capability of 4D-STEM to provide statistically robust, mesoscale insight into complex phase-evolution processes in LMR cathodes.
4D-STEM↗