bluuebunny/crossref_metadata_2025 huggingface dataset:
Atomic Layer Deposition of ZnO on the 3D Porous Ni(OH)2 Nanostructure for Supercapacitor Applications
Authors: Ji-Hu Baek , Kwon Se-Hun
Published: November 2022

Atomic Layer Deposition (ALD) is a unique vapor-phase non-line-of-sight deposition process, it can provide excellent control over the wall thickness of nanostructures at the sub-angstrom scale and can be used to create highly conformal coatings of dense inorganic film even on the nano-sized templates with high aspect ratios. Due to these inherent merits, it has become an inevitable process in current semiconductor industries. Following the success of ALD in the semiconductor industries, ALD is recently focused because it can efficiently enhance the performance of energy conversion and storage devices.

As a representative example, electrochemical supercapacitors, as one type of novel power device, have attracted universal research interest because of their great potential to be applied in many fields. In particular, pseudocapacitor is recently focused due to its larger capacitance. The electrochemical energy conversion and storage performance of pseudocapacitors depends strongly on the intrinsic properties of the active electrode materials and their surface area. To maximize these performance, various nano-morphologies and transition metal oxides/hydroxides, such as NiO, Co3O4, MnO2, Ni(OH)2 and etc., having a large theoretical capacitance has been extensively investigated. Those psuedocapacitor materials, however, generally showed a high electrical resistivity and it remain unable to achieve high theoretical capacitance in practical applications.

To solve these drawbacks, ultrathin conductive ALD coatings can be considered. As a representative example, we design and fabricate a novel hybrid 3D Ni(OH)2@ZnO nanostructured electrode material with a high surface area and high conductivity using a hydrothermal method and ALD. ALD-ZnO thin films were deposited on the surface of a 3D porous Ni(OH)2 nanostructure. The optimization of ALD-ZnO was performed to achieve a high conductivity and electrochemical performance. And, it was exhibited that this hybrid 3D core-shell structure, which benefits from the synergistic effects of both Ni(OH)2 and ZnO, can result in a much improved supercapacitor performance.
(Invited) Area-Selective Spatial Atomic Layer Deposition of Silicon-Based Materials
Authors: Mameli Alfredo , Karasulu Bora , Shen Jie , Roozeboom Fred
Published: November 2022

Area-selective atomic layer deposition (AS-ALD) holds great potential for advancing device manufacturing.1 Recently, outstanding progress on this topic has been made in terms of understanding and developing highly selective processes for various material systems; some of these processes have already been transferred into fabs.2

In this work we provide an overview of AS-ALD of silicon-based materials with high selectivity and high throughput, especially silicon oxide and nitride. While the selectivity is mostly governed by the method of choice and the underpinning chemistry, the aspect of high-throughput is ensured by using spatial ALD, which is, in our case, performed at atmospheric pressure.

The processes presented here comprise three steps: selective inhibitor chemisorption, plasma-based spatial ALD and spatial back-etching. Particular focus is given to the choice of inhibitors as the most critical step in enabling high-selectivity. Here, density functional theory (DFT) calculations have been employed to unveil the chemistries governing the selectivity for the two different inhibitors within the same growth system. General guidelines on the inhibitor chemistries are derived by combining experimental and DFT results.

Finally, process details and effect of plasma chemistries on different surfaces are discussed in an effort to expand the selectivity toolbox to other silicon-based materials.

[1] A. Mameli, et al., “Area-Selective Atomic Layer Deposition of SiO2 using acetylacetone as a chemoselective inhibitor in an ABC-type cycle”,
ACS Nano, 11, 9303, 2017.

[2] H.-P. Chen, , et al., “Fully Self-Aligned Via Integration for Interconnect Scaling Beyond 3nm Node”, IEDM 2021, paper 22-1.

Figure 1
(Invited) ALD Coatings for Li-Ion Battery and All-Solid-State Battery Applications
Authors: Kitsche David , Kondrakov Aleksandr , Janek Jürgen , Brezesinski Torsten
Published: November 2022

Lithium-ion batteries (LIBs) are essential for modern life, and their improvement is crucial for the more widespread adoption of electric vehicles.[1] Layered lithium transition metal oxides, such as LiNixCoyMnzO2 (often referred to as NCM or NMC), are among the most widely used cathode active materials (CAMs) for automotive applications, owing to their technological maturity and high energy density. However, they typically require a surface coating for stabilizing interfaces, both in liquid-electrolyte based LIBs and in solid-state battery (SSB) environments. For the preparation of protective CAM coatings, atomic layer deposition (ALD) stands out with its ability to produce conformal films on complex substrates.

This presentation encompasses several examples of successful improvements in cycling performance of Ni-rich NCM CAMs in LIBs and SSBs by ALD of binary oxides. The low-temperature deposition of AlxOy onto ready-to-use cathode sheets will be discussed.[2] ALD or ALD-related surface protection enables increased stability by suppressing detrimental surface corrosion and metal leaching (side reactions) in LIBs.[2,3] Moreover, we report about the application of ALD coatings to Ni-rich NCM CAMs in SSBs with lithium thiophosphate solid electrolytes. Specifically, the effect that both HfO2 and ZrO2 have on the cell cyclability will be shown, with emphasis placed on the role of post annealing.[4]

[1] Goodenough et al. J. Am. Chem. Soc. 2013, 135, 1167.

[2] Neudeck et al. Sci. Rep. 2019, 9, 5328.

[3] Neudeck et al. Chem. Commun. 2019, 55, 2174.

[4] Kitsche et al. ACS Appl. Energy Mater. 2021, 4, 7338.
Conversion Reactions and Redox Changes on the Surface of Lithium-Ion Battery Cathode Materials during Chemical Vapor Treatment for ALD
Authors: Darapaneni Pragathi , Mane Anil U. , Hood Zachary D. , Elam Jeffrey W.
Published: November 2022

Atomic layer deposition (ALD) has emerged as a promising technology for applying ultrathin protective coatings on lithium-ion battery (LIB) cathode surfaces to improve their cycling stability. While there have been numerous reports evaluating the electrochemical performance of these surface-modified cathode materials, the chemical changes induced on the surface of the cathode materials by the ALD coatings and the individual ALD precursors are not fully studied. We performed a systematic investigation to understand the interfacial changes of 12 different cathode materials upon coating with aluminum oxide (Al2O3) using trimethyl aluminum (TMA) and H2O, and aluminum fluoride (AlF3) using TMA and hydrogen fluoride pyridine (HFPy). We also explored the effects of the individual TMA and HFPy precursors on the cathode surfaces. The surface composition and microstructure of these cathode materials, which range from simple transition metal oxides (e.g., NiO and MnO) to complex multi-element cathode materials (e.g., LiNixMn1-x-yCoyO2, NMC), were studied via X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). The XPS measurements reveal that the transition metals in the cathode materials undergo selective oxidation/reduction depending upon the nature of the precursor, the coating, and the cathode material. Furthermore, XPS and STEM measurements show the conversion of surface carbonate species to the corresponding metal fluorides upon HF exposure. This conversion reaction is self-limiting but extends hundreds of nanometers below the surface in the case of Li2CO3. ALD and chemical vapor treatment provide new avenues to systematically control the interface of the cathode materials in LIBs that are not possible by conventional coating methods.
(Digital Presentation) Simultaneous Transforming Residual Lithium Compounds and Stabilizing Surface Lattice Oxygen for Ni-Rich Cathode Via Atomic Layer Deposition and Post-Annealing
Authors: Li Jiawei , Yi Ge , Xiang Junren , Shao Huachen , Liu Xiao , Shan Bin , Chen Rong
Published: November 2022

Unstable surface species such as residual lithium compounds and surface lattice oxygen at charge state are detrimental factors for the battery performance of Ni-rich cathode (LiNixCoyMn1−x−yO2, x ≥ 0.6, NCM), which induce serious side reactions and lead to rapid capacity loss during cycling. With the advantages of sufficient contacts between gas and solid, gas reactants are introduced to reducing residual lithium compounds via gas-solid reactions or building protective coatings to isolate surface lattice oxygen from the electrolyte via gas-phase deposition, which effectively enhances the cycling stability of NCM. Atomic layer deposition (ALD), as a special coating technology, possesses both the nature of the gas-solid reaction and gas-phase deposition. It is significant to investigate the mechanism of ALD in enhancing the cycling stability of NCM.

Here, we report a method to improving the rate capacity and cycling stability of single-crystal NCM via Al2O3 and B2O3 ALD by constructing a highly Li-ions conductive and electrochemical stable surface. The ultrathin coatings are uniformly coated on the surface of NCM. Moreover, surface composition characterizations show the reductions of residual lithium compounds and formations of lithium-containing coatings after the ALD process. By adding a post-annealing process, Al3+ cations and BO3- polyanions doping form on the surface of NCM, which robustly enhanced the stability of surface lattice oxygen of NCM via strong Al-O bond and B-O bond. Moreover, as acidic oxides, B2O3 shows better performance than Al2O3 in reducing residual lithium compounds during the ALD process. Different from Al3+ cations doping occupying the transition metal ions position, BO3- polyanions doping occupies the oxygen ions position, which does not deteriorate the capacity of NCM. Transformation of residual lithium compounds and stabilizing surface lattice oxygen on NCM greatly decrease the formation of LiF and degradation of surface structure, which is the key to the improvement of rate capacity and cycling stability.
(Invited, Digital Presentation) Atomic Layer Deposited Templates for Constructing Functional Metal-Organic Framework Thin Films
Authors: Zhao Junjie
Published: November 2022

Metal-organic frameworks (MOFs) are a class of porous crystalline materials featuring high surface area, ordered pore structures and amenability for post-synthetic modification. Integrating MOF thin films with various substrate materials could enable applications in separations, heterogeneous catalysis, chemical sensors and electronic devices. However, it is difficult to find a universal approach to deposit uniform and high-quality MOF coatings on a variety of substrate materials. Previous attempts often require surface modification methods that may not be generally applicable.

In this talk, interfacial engineering using atomic layer deposited (ALD) templates will be discussed for forming MOF thin films on various substrates. We found that ALD metal oxides are effective in promoting the heterogeneous nucleation of MOFs and also readily hydrolyzed into hydroxy double salts (HDSs) for rapid transformation to MOFs. With ALD template layers, conformal and functional MOF coatings were integrated on fibers, membranes and laminated structures. Accordingly, we developed a series of MOF-functionalized fibers for adsorption and catalytic degradation of hazardous compounds. Furthermore, we obtained ultra-thin mixed-metal MOF skin layers on porous alumina supports for membrane separation, and achieved large propylene permeance (up to 4.5×10-8 mol·m-2·s-1·Pa-1) and high propylene/propane selectivity over 250. We anticipate that this platform technology will also lead to potential device structures for chemical sensing, energy storage and many other scenarios.
Solution ALD: A Versatility Process for the Growth of Sulfides and Selenides
Authors: Barr Maissa K. S. , Zhao Baolin , Von Grundherr Peter , Koch Vanessa , Charvot Jaroslav , Halik Marcus , Bures Filip , Bachmann Julien
Published: November 2022

We have proposed and demonstrated a novel thin film deposition technique by transferring the principles of atomic layer deposition (ALD), known with gaseous precursors, towards precursors dissolved in a liquid. The technique can also be considered as a generalization of already established methods such as the ‘layer by layer’ growth or the ‘successive ion layer adsorption and reaction’ (SILAR). 'Solution ALD' (sALD) shares the fundamental properties of standard ‘gas ALD’ (gALD), specially the self-limiting growth and the ability to coat conformally deep pores. It has been already shown that it is possible to transfer standard reactions from gALD to sALD such as TiO2 deposition . However, sALD also offers novel opportunities such as overcoming the need for volatile and thermally robust precursors.

To illustrate this, we establish sALD procedures for depositing films of non oxides layers such as Pb-compound deposition, MOF, selenides and sulfides. Those examples highlight how ionic, polar, or high-molecular weight precursors that only exist in the condensed phase are now rendered amenable to being utilized in surface-controlled thin film formation by sALD for depositing materials that would otherwise be more difficult or more expensive to achieve by gALD or hazardous. The deposition was achieved on small (2 cm*1 cm) and large samples (up to 10 cm*10 cm). The ALD behavior has been shown. The influence of the deposition parameters on the morphology, the crystalline structure and the chemical composition has been investigated by scanning electron microscopy, atomic force microscopy, grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy. Additionally, the nucleation is studied in function of chemical pretreatment to control the growth and allow selective deposition of SnS, SnSe and Sb2Se3.

This particular ALD process offer the growth of high quality and crystalline layers in middle conditions with the use of low cost and environmental friendly precursors.

Y. Wu, D. Döhler, M. Barr, E Oks,M. Wolf, L. Santinacci and J. Bachmann, Nano Lett.
2015, 15, 6379

J. Fichtner, Y. Wu, J. Hitzenberger, T. Drewello and J. Bachmann, ECS J. Solid State Sci. Technol.
2017, 6, N171
Crystallization Kinetics in Atomic Layer Deposited (ALD) Thin Films: Opportunities of Time and Chemical Environment
Authors: Losego Mark D , Wooding Jamie
Published: November 2022

Atomic layer deposition (ALD) frequently produces amorphous films, however crystalline phases are often desired for various electrical, chemical, and optical applications. Thus, understanding the fundamental crystallization kinetics of films deposited by ALD is important in designing process pathways to achieve low-temperature crystallization, ultra-thin film (<50 nm) crystallization, controlled microstructures, and epitaxial growth. This presentation will discuss our work to study the crystallization kinetics in ALD TiO2 thin films and challenge some pre-conceived notions about thickness and temperature requirements for ALD film crystallization. We will focus on a prototypical TiO2 ALD process using tetrakis(dimethylamino)titanium(IV) (TDMAT) and water at between 140 °C and 220 °C. Initially, we will discuss data collected on post-deposition, isothermal crystallization kinetics at temperatures ranging from 140 to 200 °C. These time-dependent transformation kinetics are fit to the Johnson-Mehl-Avrami-Kolmogorov (JMAK) model, revealing a continuous nucleation process and a two-dimensional growth mechanism, consistent with the observed grain sizes. We also use images collected over short annealing times to independently determine the crystal nucleation rate, which allows us to determine that the activation energies for nucleation (1.32–1.35 eV K-1 atom-1) are about one order of magnitude greater than the activation energies for grain growth (0.12–0.24 eV K-1 atom-1), sugggesting that nucleation is the more significant barrier to crystallization in this system. Finally, we will show how a modification to the process’s chemical environment can lower this barrier to nucleation leading to dramatic in situ crystallization (with no post-deposition annealing) at unusually low process temperatures and film thicknesses (< 15 nm).
(Digital Presentation)Cu Coordination Environment Modification Via Atomic Layer Infiltration As High Selective CO2RR Catalyst
Authors: Cao Meng , Han Xueyang , Liu Zhang , Ren Haonan , Du Chun , Yang Fan , Shan Bin , Chen Rong
Published: November 2022

Carbon dioxide (CO2) is the most notorious greenhouse gas, released by both natural and artificial processes. In an ideal scenario, the production and consumption of CO2 should be balanced so that the concentration of CO2 in atmosphere remains constant to maintain environmental stability. Unfortunately, with the intensification of human industrial activities, this balance has gradually been disrupted, leading to more CO2 production and making global warming a pressing issue. With carbon neutrality gaining increasing attention, electrochemical CO2 reduction reaction (CO2RR) has emerged as a research orientation which converts CO2 to value-added products while storing renewable energy. Cu-based electrocatalysts have been studied extensively for the CO2RR into hydrocarbons in aqueous solutions under environmental conditions. However, they frequently endure low Faradaic Efficiency (FE) and selectivity of specific single product. Particularly, precise construction of Cu micro-environment is of great challenge for the design and fabrication of excellent Cu-based CO2RR catalysts.

Atomic layer infiltration (ALI) allows gas phase precursors to penetrate and diffuse into porous substrates through their nanoporous structures and to grow within the subsurface. Aiming at systematically regulating the Cu metal site micro-environment, porous HKUST-1 containing paddle-wheel Cu coordination nodes was chosen as a template and modified with ALI technique in this work. Various metals were introduced into HKUST-1 using ALI method to construct bimetallic sites which tended to produce CO, HCOOH and other products with high FEs. Density Functional Theory (DFT) calculations prove the modification with metals by ALI enhances the adsorption enthalpy of CO2 and alters the bonding interaction between reaction intermediates and adsorption center, thereby changing the reaction pathways. MOF conversion technique based on atomic layer deposition (ALD) will be utilized to fabricate HKUST-1 thin film in our future work, which allows nanometer precision of catalyst loading to balance active-site density with mass/charge transfer. The proposed ALI and ALD techniques elucidate the reliance of CO2RR selectivity on the Cu micro-environment and provide a platform for regulating Cu or other metal-base electrocatalyst coordination environment to facilitate high selectivity of CO2RR in the future
Silane-Based Surface Treatments for Area Specific Deposition
Authors: Brick Chad , Liberatore Richard , Goff Jonathan
Published: November 2022

In material science, silicon-based molecules are staple reagents for applications such as self-assembled monolayer formation, reduction of surface energy, and modification of surface chemistry for secondary functionalization reactions. In our presentation, we will review organosilanes in the context of Area Specific Deposition (ASD), with a particular emphasis on cyclic azasilanes. Compared with more traditional linear chlorosilane and aminosilane-based surface treatments, cyclic azasilanes offer extremely rapid (<5 second) deposition times over a broad temperature range without any volatile chemical by-products. The interaction of cyclic azasilanes with various oxide and metal substrates will be discussed in relation to the plasma, thermal, or wet methods used to condition the surfaces for deposition. Furthermore, we will discuss the ability of the resulting silane monolayer films to block deposition of common organometallic ALD precursors in relation to deposition process conditions. In conclusion, we will demonstrate the resulting dielectric-on-dielectric and dielectric-on-metal deposition schemes.
Modeling Onset of Lithium Plating on Porous Graphite Anode in Fast Charging
Authors: Lian Huada , Bazant Martin
Published: November 2022

Lithium plating is one major degradation mechanism of the anode in lithium-ion batteries. The redox potential of graphite, the most widely used anode material, is 0.1V vs. Li+/Li, thus making parasitic Li plating inevitable during operation without precise control. Capturing the onset of lithium plating on graphite on the fly usually relies on both experimental and modeling techniques. We combine the phase-field approach and a hierarchical porous electrode theory to capture the dynamics of reaction and transport in the porous graphite electrode. The model is validated against the lithiation dynamics of porous graphite anode measured in-operando, capturing both the spatial and temporal non-uniformity. We then parameterize the model to a Li/Graphite half-cell setup and find a good agreement of materials-related parameters obtained across multiple datasets. The model respects the reaction kinetics and transport in a phase-separating material, thus transferable, and can guide the experimental design of battery and characterization methods for early detection of lithium plating.
Data Driven Model for Lithium-Ion Battery Electrode Microstructure Property Estimation
Authors: Kabra Venkatesh , Kamboj Ishita , Augustyn Veronica , Mukherjee Partha P.
Published: November 2022

Li-ion batteries (LIB) are ubiquitous in today’s world with applications ranging from portable electronic devices to electric vehicles. These set of applications require the batteries to have diverse energy and power dense configurations. For these reasons the LIB exists in multiple form factors such as cylindrical, pouch cell configurations and different chemistries. The most commercialized and successful LIB are based on intercalation mechanism, which requires shuttling of Li-ion between anode and cathode with redox reaction occurring on the surface of the electrodes and ultimately leading to the Li-ions to diffuse into the host structure of the electrode. Such electrodes are naturally made to be porous, to maximize the surface area for redox and electrochemical reaction, also giving rise to multiple pathways for Li-ion diffusion and migration. These electrode structures are also integrated with additives to increase the electronic conductivity and mechanical strength. This gives rise to the microstructure as a matrix of different phases with multi-length scale structure and characteristics at different scales. The performance and operation of battery is closely intertwined with these electrode microstructure, and thus microstructural characteristics significantly influence the transport process or kinetics of the reaction. This relation between performance and electrode microstructure is not limited to the composition of electrode rather even with fixed chemical composition the widely different structural arrangement of the phases alters the short- and long-range interactions within the electrode. Specifically based on electrochemical performance model, the electrochemical-thermal interactions can be captured with few important effective electrode properties such as interfacial area, tortuosity and conductivity. Here we develop a framework for the accurate prediction of these effective electrode properties as a function of the microstructural properties. For this purpose of effective electrode property prediction, we develop an integrated framework, including information from the physics informed mesoscale model along with the data driven models. The accurate effective electrode properties are evaluated from pore-scale characterization of microstructure, to serve as output for data set. Our main objective with developing such a framework is to describe the effective electrode properties with simple yet meaningful correlations, which can accurately capture physics while maintaining high predictive accuracy, thus also providing directions for better electrode manufacturing.
An Efficient Electrochemical State of Health Model for Lithium-Ion Batteries
Authors: Lim Jin-hyung , Uppaluri Maitri , Subramaniam Akshay , Subramanian Venkat R.
Published: November 2022

Capacity fade experienced by the battery will affect the lifetime of the battery pack as well as the residual value of an electric vehicle. Developing a degradation model that can prognosis state of health for the given operating condition is critical for developing an algorithm to maximize the remaining useful lifetime of the systems. It is known that the electrochemical degradation model has superior predictability to other data-driven models, but still needs improvement in terms of computational efficiency. We reduced the electrochemical degradation model which considers three main aging mechanisms that can predict the state of health at various calendric aging conditions. The parameterization procedure and its prediction capability will be also discussed.
Enhancing Lithium-Ion Battery Aging Simulations By Coupling a High-Resolution, 3D, Grain-Scale Electromechanical Model to a Single Particle Model
Authors: Allen Jeffery M. , Weddle Peter J , Usseglio-Viretta Francois L. E. , Verma Ankit , Colclasure Andrew M. , Smith Kandler
Published: November 2022

One of the main goals in modeling lithium-ion batteries is to improve/predict longevity and resilience of new chemistries. Unfortunately, this requires simulation of thousands of charge/discharge cycles, which can be rather time consuming depending on the fidelity of the simulation. The purpose of this talk is to discuss a new modeling framework that couples a high-resolution, continuous damage model (CDM) to a single particle model (SPM) resulting in a good combination of speed and fidelity.

In previous work, a 3D, continuum-level chemo-mechanical model was developed to investigate cracking within a single cathode particle comprised of hundreds to thousands of randomly oriented grains. The CDM predicted that particle fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. Essentially, when neighboring grains were misaligned, they expanded different rates relative to one another leading to high stresses and ultimately the formation of intraparticle cracks. The model predicted that small particles with large grains develop significantly less damage than larger particles with small grains. Finally, the model predicted most of the chemo-mechanical damage accumulates in the first charge after formation. This chemo-mechanical “damage saturation” effect indicated that initial particle fracture occurs within the first few cycles, while long-term cathode degradation is not solely chemo-mechanically induced. This led to a need for simulating fatigue-like mechanism that degrade the battery over longer time scales.

In order to reach the time scales, need to resolve fatigue-like degradation, the CDM needs to be complemented by a faster model. Therefore, recent efforts have been focused on using results from the CDM to inform parameters within the SPM. These parameters are homogenization factors that are associated with diffusion, particle radius, and/or exchange current density. By coupling the CDM to the SPM, the aging simulation is broken up into two domains: short-term and long-term degradation. The short-term degradation occurs over a single cycle and is handled by the CDM due of its high fidelity, but relatively expensive computational cost. Such mechanism include break-in crack caused by mismatches in grain orientation. The long-term degradation occurs over tens of cycles and is handled by the SPM due it’s computational efficiency. Most of the fatigue-like mechanism fall into this category.

The eventual goal of this modeling framework is to upscale to a psudo-2D model allowing for full electrode simulation, which are informed by high-fidelity grain-scale simulations.

Figure 1
Impact of Data Window on Prediction of Battery Aging and Swelling
Authors: Pannala Sravan , Siegel Jason , Stefanopoulou Anna
Published: November 2022

Lithium-ion batteries degrade over time, based on their usage and these changes can be observed in the terminal voltage and cell expansion curves with respect to SOC. Physics-based battery models augmented with degradation modes can describe the changes in battery electrical and mechanical response as the battery ages and can be tuned to predict the observed rate of change. Tuning these models is computationally intensive, because it requires multiple simulations of the battery aging process over the entire lifetime. Accelerated simulations that use an adaptive inter-cycle extrapolation algorithm [1] can reduce simulation time and thus enable use of optimization algorithms to automatically tune degradation models [2].

In this work, we investigate how the amount of aging data used to train the model impacts the prediction of future battery aging assuming the battery continues to operate under the same conditions. The electrode-specific state of health (eSOH) parameters are computed from the reference performance testing performed at periodic intervals throughout the battery's lifetime. These four parameters include the capacities of positive and negative electrodes Cp and Cn, and the corresponding electrode stoichiometric windows y0 and x100. These 4 parameters extracted from a cell aged at C/5 constant current charging rate were used for training the model.

The aging model includes SEI growth in the negative electrodes which causes a loss of cyclable lithium/loss of lithium inventory (LLI) and loss of electrode active material (LAM) due to particle cracking at both the negative and positive electrodes. Simulation results show us that a shorter training window of three eSOH reference points (every 25 cycles) over (Cycles 41 to 98) over-predicts battery degradation because the rate of degradation during these initial cycles is larger than the degradation which happens later in the battery's life. The battery degradation parameters that are predicted (and shown in the figure) include battery capacity, maximum reversible swelling in the battery, loss of active material in the negative electrode and loss of lithium inventory. If we increase the model training window to five eSOH data points (Cycles 41 to 175), the prediction of battery degradation is much better because the model now accounts for both the initial higher rate of degradation and subsequent lower rate of degradation.

References:

V Sulzer et al. Accelerated Battery Lifetime Simulations Using Adaptive Inter-Cycle Extrapolation Algorithm, Journal of Electrochemical Society (2021)

S. Pannala et al. Methodology for Accelerated Inter-Cycle Simulations of Li-ion Battery Degradation with Intra-Cycle Resolved Degradation Mechanisms, American Controls Conference (2022)

Figure 1
A Battery Aging Mode Identification Framework: Encompassing Multiple Cell Chemistries, Electrode Designs, and Use Conditions
Authors: Chen Bor-Rong , Walker Cody M. , Kunz M. Ross , Tanim Tanvir R. , Dufek Eric J.
Published: November 2022

A key challenge for Lithium-ion batteries (LiB) is the capability to manage battery performance and predict the battery’s lifetime, which are crucial information for optimum operation of electric-vehicles (EVs). In that regard, early detection of battery-aging phenomena and their implications on performance is necessary for maintaining warranty and avoiding safety-related liabilities. However, rapid diagnosis of the root causes of battery degradation has not yet been well-developed nor studied upon a broad mixture of cell designs and use cases.

Here, a machine-learning (ML)- based framework is presented that aims at identifying aging modes or mechanisms during battery cycling. Cycle-by-cycle electrochemical signatures (e.g., end-of-rest voltages, columbic efficiency, and capacity fade) were analyzed then correlated with aging modes, such as loss of active materials in the cathode (LAMPE) or loss of Li inventory (LLI). Multiple battery designs and use conditions were analyzed to develop this ML framework, including 44 single layer pouch cells representing two cathode chemistries (NMC532 and NMC811), two electrode loadings (low and moderate), and five charging rates (1, 4, 4.5, 6, and 9C CC-CV profiles). Predominant aging behaviors depend on both the cell design and use. Aging behaviors can be classified into a combination of LAMPE and LLI. A classification accuracy of 90% was achieved using only the first 200aging cycles, and the percentage of LAMPE was predicted with 4.3% of error after 600 cycles. As seen here, the overall aging behavior of the battery was found to be dependent on cathode chemistry, electrode build, and usage conditions.

This ML framework is promising for battery developers to save the time and effort that is typically associated with prolonged testing. The ML framework will also advise on innovative design strategies to counter specific degradation modes, thus significantly accelerating the development cycle for building longer lasting batteries. From the end user’s perspective, this aging-mode diagnosis framework enables the ability to fine-tune battery service scenarios to minimize degradations thereby improving both lifetime and safety in EVs or stationary storage systems.

Figure 1
Isoxazole-Based Electrolytes for Lithium Metal Protection and Lithium-Sulfurized Polyacrylonitrile (SPAN) Battery Operating at Low Temperature
Authors: Tan Sha , Liu Haodong , Wu Zhaohui , Ronne Arthur , Shadike Zulipiya , Liu Ping , Hu Enyuan , Yang Xiao-Qing
Published: November 2022

A new electrolyte system using isoxazole as the salt dissolving solvent has been developed and studied for lithium metal batteries. By using fluoroethylene carbonate (FEC) as an additive and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) as a diluent for localized high concentration electrolyte (LHCE), isoxazole-based electrolytes were successfully implemented in lithium metal batteries, demonstrating excellent lithium metal protection capability. Utilizing several advanced characterization techniques (including synchrotron-based X-ray absorption spectroscopy and photoelectron spectroscopy), the solid electrolyte interphase (SEI) formed on the Li-metal anode in cells using these electrolytes was thoroughly investigated. The high ionic conductivity of isoxazole at low temperature and the low impedance of SEI formed in LHCE significantly improved the low-temperature performance of Li-sulfurized polyacrylonitrile (SPAN) batteries, delivering 273.8 mAh g-1 capacity at -30°C with 99.85% capacity retention after 50 cycles.

Acknowledgment: The work done at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program, including Battery500 Consortium under contract number DE-SC0012704. This research used beamline 8-BM (TES) and 7-ID-2 (SST-2) of the National Synchrotron Light Source II, U.S. DOE Office of Science User Facilities, operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704. SEM measurements for this manuscript were performed at Center for Functional Nanomaterials, a U.S. DOE office of Science User Facility, at Brookhaven National Laboratory under the contract number DE-SC0012704.
Electrolyte Development for Fast Charging of High Energy Density Li-Ion Cells
Authors: Du Zhijia
Published: November 2022

Different lithium salt concentrations in carbonate electrolyte were studied on the fast charging performance of LiNi0.6Mn0.2Co0.2O2 (NMC622)/graphite pouch cells. The cells with electrolyte concentration from 0.75 M to 1.50 M showed similar fast charging capabilities. Further increase of the concentration to 1.75 M and 2.00 M decreased the attainable capacity in fast charging. In the long-term cycling test, the capacity retention after 200 fast charging cycles increased with the increase of salt concentration in electrolyte. Cells with 1.5 M electrolyte showed the best overall performance in fast charging capacity and long-term cycling. Li plating were observed in the cells with 0.75 M, 1.00 M and 1.25 M electrolyte. It was improved with greatly reduced Li plating area in 1.50 M, and no Li plating at all in 1.75 M and 2.00 M electrolyte. Post-mortem analysis such as neutron powder diffraction (NPD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the electrode after cycling. It suggests that electrolyte concentration needs to be optimized for a given cell configuration with specific electrode and loading.

Figure 1
Simulations and Analyses of Li4 and Li6 Boracites and Thioboraocites As Promising Li Ion Conducting Electrolytes
Authors: Lynch David , Li Yan , Holzwarth Natalie
Published: November 2022

The naturally occurring magnesium borate mineral, Mg3B7O13Cl, is characterized by a rigid

framework of B-O bonds together with a regular void structure, ideally forming crystals in the

face-centered cubic structure and characterized by the space group F-43c (#219). Recently,

several structurally related Li ion conducting boracites and thioboracites have been synthesized

and computationally investigated, including Li4B7O12Cl [1], Li4Al3B4O12Cl [2], and Li6B7S13I [3].

The high ionic conductivity of all of these materials is related to the occurrence of natural

interstitial Li sites due to the high symmetry of the crystalline structures. In this presentation, we

report the results of computational analysis and simulations of the large family of Li4 and Li6

ion-conducting boracites and thioboracites, including the experimentally identified materials and

several computationally predicted materials. The simulation results provide guidance on the

detailed mechanisms of Li ion mobility, the stability of materials with respect to decomposition,

and the structural stability of the materials with respect to rhombohedral and other distortions.

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[1] Y. Li and N. A. W. Holzwarth, Phys. Rev. Materials 6, 025401 (2022)

https://doi.org/10.1103/PhysRevMaterials.6.025401.

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https://doi.org/10.1021/jacs.1c00941.

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The work was supported by NSF Grant No. DMR-1940324. Computations were performed on the Wake Forest University DEAC cluster, a centrally managed resource with support provided in part by the university.
(Digital Presentation) Comparative Reliability Testing of Li-Ion Battery Chemistries Under Grid Services
Authors: Choi Daiwon , Kim Namhyeong , Shamim Nimat , Crawford Alasdair , Viswanathan Vilayanur , Modachur Sivakumar Bhuvaneswari , Huang Qian , Thomsen Edwin , Reed David , Sprenkle Vincent
Published: November 2022

Li-ion batteries are the most widely deployed battery energy storage system (BESS) today but understanding the benefits and cost effectiveness for a wide range of grid services needs to be validated for market expansion. In this work, commercially available cylindrical cells with four different chemistries from major Li-ion battery manufacturers are subjected to standardized tests developed by the U.S. Department of Energy Office of Electricity (DOE-OE) for frequency regulation, peak shaving, and electric vehicle drive cycles. The results of preliminary 15 months continuous grid service tests on four different chemistries are presented and compared in terms of capacity retention, resistance, open-circuit voltage (OCV), cyclic voltammetry (CV), dV/dQ, and AC impedance.
(Digital Presentation) A Polymeric/Inorganic Composite Coatings on the Separator for High-Energy Lithium Metal Battery
Authors: Ni Jie , Xiao Qiang Feng , Lei YiKE , Han YongKang , Zhang YingChuan , Geng Zhen , Zhang Cunman
Published: November 2022

Lithium metal (Li) is a highly promising anode for next-generation rechargeable due to its high specific capacity (3,860 mA/g) and low negative electrochemical potential (-3.040 V vs. the standard hydrogen electrode). However, the issues such as high reactivity with electrolyte, infinite volume expansion, and uneven Li plating/stripping, cause low Coulombic efficiency, unstable growth of the solid-electrolyte interphase (SEI), and lithium dendrites. SEI plays an important role in the stabilization of lithium metal anodes in rechargeable batteries. Here we report a polymeric inorganic composite coatings (PICC) on the Celgard separator to regulate the Li-ion transport during charge/discharge of the battery. Such coatings enable uniformly deposition of Li, form a stable SEI film and in turn improve the electrochemical performance of the rechargeable batteries. Firstly, poly(vinylidene ﬂuoride) (PVDF) and Li6.03La3Zr1.75Nb0.25Al0.24O12 (LLZO) were mixed at a mass ratio of 1:2, 1:1 and 1:2 in DMF, respectively. Afterwards the mixtures were coated onto the Celgard separator using doctor blades. In the carbonate-based electrolyte, the cycle life of Li‖Cu batteries with coating (PVDF:LLZO=1:2) increases from 30 cycles for uncoated batteries to 120 cycles of and a high Coulomb Efficiency of 96% is achieved. Moreover, when a high mass loading of 15 mg/cm2 NCM811 is chosen as cathodes, the Li‖NCM811 batteries using the PICC exhibit decent rate and cycling performance. After 100 cycles, the capacity retention at 0.2C of 94% is obtained, and the specific capacity is still 191 mAh/g. These results indicate that PICC can improve the electrochemical performance of Li anodes for high-energy rechargeable lithium metal batteries.
(Digital Presentation) Using Simulations to Determine the Effects of the Lithium-Ion Battery Pack Sizes on Performance of Electric Vehicles
Authors: Liu Changhong , Sarikaya Rizacan , Chew Ismar , Robinson Nicholas Jon
Published: November 2022

Internal combustion engine (ICE) vehicles have a longer driving range with a full tank of gas than lithium-ion battery-powered electric vehicles (EVs). Alongside having a higher purchase cost and a lack of charging infrastructure, the range of EVs is a large deterrent to potential buyers. One solution to increasing the range of EVs is using a battery pack with a higher capacity. However, increasing the capacity typically involves an increase in lithium-ion battery cells, which leads to a higher weight, higher vehicle cost, lower energy efficiency, and higher battery charging time. In addition, regenerative braking recovers the vehicle's kinetic energy which is related to speed and weight. To find the optimal battery pack size, a numeric road test simulation can be used to determine how battery pack size affects energy efficiency, driving range, charging time, and cost. This is more optimal than a real-life road test since inconsistent variables like traffic conditions and weather can be controlled. This paper applies work-energy mathematic modeling of an electric vehicle under different EPA dynamometer driving schedules to investigate the problem proposed above, using an EV model with 21700 type lithium-ion cells. In addition, total vehicle weight, motor efficiency, wheel sizes/weight, and the weight of passengers will also be considered. The simulation revealed that when the total vehicle weight reaches a certain point, it can regenerate significant kinetic energy back to the battery pack to increase the range.

Figure 1
(Digital Presentation) Improvement of 280mAh/g - Class Li(1+x)(Ni0.15Mn0.8Co0.05) (1-x)O2 Cathode Material
Authors: Nakamura Hitoshi
Published: November 2022

Li-rich Li2MnO3-LiMO2 solid solution positive electrode materials are expected to insist high capacity and have been actively studied in recent years. In this paper, we will review various characteristics of Li(1+x)(Ni0.15Mn0.8Co0.05) (1-x)O2. The sample showed a discharge capacity of 300 mAh / g or more on the initial charge at 4.8 V. After that, it showed stable charge / discharge characteristics at 4.6V. As a result of XRD analysis, a peak derived from the (-Mn-O or Li-Mn-) n honeycomb structure was observed near 20 °(2θ). When the molar content of Li was measured by ICP, it was found that Li was contained at 1.67 with versus to the transition metal, suggesting that a solid solution was formed.

Figure 1
Ionic Liquid-Based Electrolytes for the Long-Term Cycling of High-Voltage Lithium-Based Cathode Materials
Authors: Wu Fanglin , Kuenzel Matthias , Kim Guk-Tae , Passerini Stefano
Published: November 2022

High-voltage cathode materials, granting high-energy density lithium batteries, face the challenge of developing functional electrolytes enabling their stable operation at voltages higher than 4 V (vs. Li+/Li). Non-volatile and poorly flammable ionic liquid electrolytes (ILEs) are successfully applied to overcome this challenge, even with low-Co or Co-free positive electrode materials. With the ionic liquid-based electrolytes, the cathodes exhibit remarkable electrochemical performance, achieving initial specific capacity above 200 mAh g-1 and outstanding capacity retention (up to 88% over 1000 cycles). More importantly, these electrolytes enable average Coulombic efficiency as high as 99.94%. The excellent compatibility of the ILEs with the high-voltage positive electrode materials enables the realization of cells achieving rather high specific energies.