bluuebunny/crossref_metadata_2025_split huggingface dataset:
Looking for the Lost Lithium: Lithium Trapping and Its Effect on Capacity Losses in Li-Ion Batteries
Authors: Rehnlund David , Lindgren Fredrik , Pan Ruijun , Huang Yu-Kai , Wang Zhaohui , Nyholm Leif 
Published: May 2020

Rechargeable lithium batteries are well-known to exhibit progressive capacity decays upon cycling, leading to loss of cell voltage, power and energy. However, the origins of capacity losses are still not fully understood and are largely attributed to the formation of a solid electrolyte interface layer and volume expansion. Another largely overlook capacity decay mechanism is lithium trapping 1–4. Lithium trapping, caused by incomplete delithiation, is here demonstrated to be the main source of capacity losses in high energy density anodes (e.g. Si) while SEI formation and dissolution affect the accumulated capacity loss due to decreased coulombic efficiency. In the following paper we will present our findings on capacity losses in standard and optimized Si-Li half cells and how these systems affect lithium trapping inside the active electrode material. We will discuss how the cycling protocol (e.g. full capacity cycling vs coulombic limited cycling) can mask signs of Li trapping and temporarily delay capacity decay in half-cells. We will highlight the importance of lithium-trapping induced capacity or voltage decays effect in lithium-based batteries, explain the mechanism for lithium-trapping and establish diffusion-controlled lithium-trapping models. Approaches toward identifying and circumventing lithium-trapping problem will also be discussed as well as challenges and proposed future research directions within this exciting and important research field.

Figure 1. Capacity evolution for an optimized nano-Silicon composite electrode in a half-cell configuration during coulombic limited cycling (i.e. 1200 mAh/g). Critical capacity decay is observed when the accumulated trapped lithium has saturated the electrode core and counteracts the deposited Li layer 1.

References

1. Lindgren, F. et al. On the Capacity Losses Seen for Optimized Nano‐Si Composite Electrodes in Li‐Metal Half‐Cells. Adv. Energy Mater.
9, 1901608 (2019).
2. Rehnlund, D. et al. Lithium trapping in alloy forming electrodes and current collectors for lithium based batteries. Energy Environ. Sci.
10, 1350–1357 (2017).
3. Rehnlund, D., Pettersson, J., Edström, K. & Nyholm, L. Lithium Trapping in Microbatteries Based on Lithium- and Cu2O-Coated Copper Nanorods. ChemistrySelect
3, 2311–2314 (2018).
4. Zhu, B. et al. Minimized lithium trapping by isovalent isomorphism for high initial Coulombic efficiency of silicon anodes. Sci. Adv.
5, eaax0651 (2019).

Figure 1
Solid-state Battery Designed For Electric Aviation
Authors: Dornbusch Donald A. , Viggiano Rocco , Dynys Frederick W. , Lin Yi , Connell John W. , Wu James J. 
Published: May 2020

The demand for higher energy density batteries increases as the demand for portable electronic devices and electric automotive increases, as well as a variety of other applications requiring substantially higher power and energy than attainable with current lithium-ion capabilities which includes the areas of high performance vehicles, military applications, and electric aviation. However, the improvement of energy density is insufficient alone for enabling electric aviation when considering the high flammability and risk of thermal runaway inherent in current state-of-the-art liquid electrolytes. The development of high energy, high power, and safe batteries are required to enable hybrid and fully electric aircraft.
Next generation chemistries such as lithium-sulfur provide high theoretical specific energy density suitable for electric aviation without as strict of volumetric requirements observed in the automotive industry. However, due to the phase transition during discharge where sulfur generates a series of soluble intermediate polysulfides, which are lost to the liquid electrolyte, cause detrimental side effects, and severely limit cycle life battery performance is severely reduced. Additionally, the low electrical conductivity of sulfur requires a large amount of inactive carbon dramatically increasing parasitic mass.
The dissolution issue make sulfur a desirable candidate to pair with a solid-state electrolyte in order to avoid polysulfide dissolution and shuttling. In addition, inorganic solid-electrolytes have low flammability providing the improved safety required. Combining this chemistry with a solid-state electrolyte provides a path for achieving the energy and safety required for electric aviation.
The development of scalable thin solid-state electrolytes paired with lithium-sulfur chemistry will be discussed and how their development will aid in enabling a unique application.
Predicting Thermal Runaway in Li-Ion Battery Employing Machine Learning Framework
Authors: Ragone Marco , Yurkiv Vitaliy , Ramasubramanian Ajaykrishna , Shahbazian-Yassar Reza , Mashayek Farzad 
Published: May 2020

Failures of lithium-ion batteries (LIBs) arise in both energetic and non-energetic ways. Both modes may occur due to numerous reasons such as cell manufacturing flaws, poor cell design (electrical or mechanical), external abuse of cells (thermal, mechanical, or electrical), defective protection electronics, chargers, etc. In this work, we present a machine learning (ML) study of the most severe energetic failure of the LIBs, which occurs due to the thermal runaway (TRA). In general, the TRA consists of a rapid self-heating of a cell sourced from exothermic (electro-) chemical reactions. During the TRA, the excessive heat has a detrimental influence on the electric characteristics and the state-of-charge (SOC) of the LIBs, which could lead to the accidental explosion of the battery. During the TRA, it is impossible to directly monitor the occurring events in practical operating conditions. However, the change of electric parameters during the TRA like-events could potentially indicate the existence of a failure, thus allowing to foresee the LIBs malfunction.
We propose two deep learning techniques to address the problem of predicting the TRA like-events based upon the temporal variation of electric parameters, the SOC and the thermal images in overheating conditions. First, a recurrent neural network (RNN) built upon the long-short-term memory (LSTM) scheme is used to estimate the time dependency of the SOC on the voltage, current and temperature of a cell. In the second method the objective is to predict the presence of the TRA in the LIBs subjected to internal/external heating directly from thermal images collected as sequences of video frames during the battery operation. For this purpose, a Convolutional LSTM (Conv-LSTM) network is constructed and trained to distinguish the recorded thermal images among two classes, specifically the presence or absence of the TRA like-events. Conv-LSTM is a recurrent neural network designed to extract information from sequential images in time series analysis, which combines the image processing capabilities of convolutional neural networks (CNN) and the temporal tracking potential of LSTM. The main advantage of the proposed techniques is that they do not require the physical modeling of the internal battery chemistry, which is cumbersome in the TRA scenario, but they rely only on the experimental/ modeling data and the collected thermal images,
Review of the Safety of Aged Li-Ion Batteries As a Function of Aging Protocol and Abuse Method
Authors: Preger Yuliya , Torres-Castro Loraine , Langendorf Jill , Lamb Joshua , Chalamala Babu R. 
Published: May 2020

High voltage and energy density have increased the use of lithium-ion batteries (LiBs) in many applications, including consumer electronics, electric vehicles, and grid-tied energy storage systems (ESS). However, with increasing energy density and installation size come heightened concerns about safety, including the risk of thermal runaway and serious fires. To understand the risks and outcomes of LiB failure, numerous studies have examined the response of fresh cells to mechanical, electrical, and thermal abuse. However, given the expected lifetime of LiBs, it is critical to consider the abuse response of aged cells. In this presentation, we review previous results on the abuse of aged cells to facilitate understanding of how aging conditions (such as temperature and cycle rate) and abuse methodology (including calorimetry, short circuit, and overcharge) impact key metrics of safety relative to fresh cells. In general, the conditions used to produce aged cells in these studies have involved extreme temperatures. Thus, we also share more recent calorimetry of cells aged to 80% capacity by relatively mild protocols to understand the abuse response of cells from more typical device operating conditions. These results facilitate a more data-informed risk assessment of aged energy storage systems and the development and adoption of appropriate failure mitigation strategies.
Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.
Parameter Identification through Physics-Based Impedance Models Using Impedance Spectra for Lithium-Ion Batteries
Authors: Teo Linnette , Kuo Jason , Hu Victor Waiman , Kolluri Suryanarayana , Pathak Manan , Schwartz Daniel T. , Subramanian Venkat R. 
Published: May 2020

Electrochemical impedance spectroscopy (EIS) is a useful characterization tool due to its ability to separate physicochemical processes by their intrinsic time constants. EIS is extensively used to study diffusion1 and kinetic2 processes, investigate passive layer growth3, and characterize aging4 in lithium-ion batteries. However, experimental EIS data is traditionally fit using equivalent circuit models with circuit elements that are representative of the physical processes happening inside a battery. Such models may lose physical meaning and interpretability as processes and parameters are lumped together.
Physics-based impedance models mathematically describe physicochemical processes based on fundamentally derived equations and are thus better alternatives for providing direct insight than their equivalent circuit analogs5. These models are often highly coupled and complex, and traditional solution methods make it difficult to solve them in a reasonable time frame suited for multi-parameter identification. Recent work on a hybrid analytical-collocation approach demonstrated significant reduction in computation time (two orders of magnitude improvement compared to commercial software), making multi-parameter estimation a more feasible optimization problem6.
Estimation of parameters is an important step to using physics-based models in battery management systems (BMS) to monitor, predict, and control batteries, since such physics-based models inherently require knowledge of specific battery parameters. This work builds on the previously developed fast simulation approach for physics-based impedance models for a full cell consisting of two porous electrodes, by conducting a parameter reduction study through clustering of physical parameters. We present a method to demonstrate the identification of parameters and explore the ability to estimate parameters for the impedance spectra at different states of charge of a cell and at various states of aging.

References

1. P. Yu, B. N. Popov, J. A. Ritter, and R. E. White, J. Electrochem. Soc., 146, 8–14 (1999).
2. K. Dokko et al., J. Electrochem. Soc., 148, 422–426 (2001).
3. E. Barsoukov, J. H. Kim, J. H. Kim, C. O. Yoon, and H. Lee, J. Electrochem. Soc., 145, 2711–2717 (1998).
4. U. Tröltzsch, O. Kanoun, and H. R. Tränkler, Electrochim. Acta, 51, 1664–1672 (2006).
5. M. Doyle, J. P. Meyers, and J. Newman, J. Electrochem. Soc., 147, 99–110 (2000).
6. M. Pathak et al., J. Electrochem. Soc., 165, A1324–A1337 (2018).
Deciphering the Role of Temperature and Thermal Gradient Magnitude on Li-Ion Battery Performance and Safety
Authors: Kingston Todd A. , Carter Rachel , Atkinson Robert W. , Love Corey T. 
Published: May 2020

Lithium-ion batteries are a transformative technology that have far-reaching implications in applications from consumer electronics to vehicles. The transient environmental conditions of many of these applications combined with internal heat generation and removal from the battery during operation cause it to be subjected to various thermal profiles. It has been shown that the cell’s material properties and kinetics are temperature dependent [1-3] and that thermal gradients can modulate electrochemistry [4, 5]. Our prior studies of externally-applied thermal gradients in batteries found that a gradient of 40 °C across the cell (0 °C anode-side and 40 °C cathode-side) has profound effects on local electrochemistry. However, the sensitivity of the cell to varied local electrode temperatures and the magnitude of the anode-to-cathode thermal gradient remains uncertain. In this work, we decipher the contributions of these two thermal aspects by independently modulating the temperature of each electrode within a single-layer pouch cell. Li-ion full cells are fabricated using lithium-iron-phosphate cathodes and graphite anodes. Local temperature measurements of the electrodes are obtained using thin-film sensors embedded within the cell. Galvanostatic cycling at different current rates and electrochemical impedance spectroscopy are performed on cells with various temperature and thermal gradient magnitudes to quantify thermo-electrochemical coupling phenomena. The implications of the thermal and operating conditions on battery performance and safety are discussed. This work demonstrates the need for effective thermal management strategies that can enable desired operational conditions, such as fast charging, while maintaining safe operation.
References
[1] Ji, Y., Zhang, Y., and Wang, C.-Y., Journal of The Electrochemical Society, 2013, 160(4), A636-A649.
[2] Love, C.T., Baturina, O.A., Swider-Lyons, K.E., ECS Electrochemistry Letters, 2015, 4(2), A24-A27.
[3] Bazinski, S.J. and Wang, X., Journal of Power Sources, 2015, 293, 283-291.
[4] Carter, R. and Love, C.T., ACS Applied Materials and Interfaces, 2018, 10, 26328-26334.
[5] Atkinson, R.W., Carter, R., and Love, C.T., Energy Storage Materials, 2019, 22, 18-28.
Unveiling the Underlying Mechanism of CO2-Assisted Li–O2 Batteries in the Presence of a Br3
–/Br2 Redox Couple
Authors: Marques Mota Filipe , Byon Hye Ryung , KIM Dong Ha 
Published: May 2020

A critical step towards the commercialization of Li-air batteries involves replacing O2 with air. The presence of CO2 in the air, however, has been established to substantially alter the O2 chemistry of the Li-air battery, emphasizing the need to pursue fundamental exploratory works prior to the development of practical devices [1]. In our preliminary studies, we have investigated the effect of an increasing CO2 incorporation in the O2 gas feed on the performance of the resulting devices with a tetraglyme-based electrolyte. When up to 30% CO2 was added to Li–O2 cells, CO2 acted as an O2
− scavenger, with emerging soluble discharge products (e.g., CO4
2− and C2O6
2−) being correlated with enhanced full capacity and cell cyclability of these devices. The CO2-assisted Li–air device was confirmed to suffer, however, from unpractical recharge potentials at ~4.5 V required for the decomposition of Li2CO3, equally formed during discharge [2]. In agreement, incorporating a Br3
–/Br2 redox mediator was proposed as a promising strategy to suppress the overcharge potential. Electrochemically-generated Br2 was shown in this work to remarkably hinder the overpotential during recharge (~0.5 V). In addition, the performance of the introduced redox mediator was disclosed to be a function of the introduced LiBr concentration and of the insulating Li2CO3 crystallinity and morphology. As a seminal methodology, coupled electrochemical and spectroscopic analyses were then pursued to discern involved redox shuttling steps at progressive states-of-charge. Remarkably, our work revealed here for the first time the presence of Br2···Br3
− loosely-bound anionic complexes in the electrolyte during the recharge step. As opposed to discrete polar Br2 irreversibly precipitated on the CNT surface, the facile diffusion of the soluble Br2···Br3
− complex pinpointed these species as operating redox mediators during cell cycling. These findings are believed to shed light over the rational design of efficient mobile mediators beyond an overcharge decrease in the unexplored CO2-assisted Li–O2 device.
References
1. Takechi, T. Shiga and T. Asaoka, Chem. Commun.
47, 3463 (2011).
2. Qiao, J. Yi, S. Guo, Y. Sun, S. Wu, X. Liu, S. Yang, P. Hec and H. Zhou, Energy Environ. Sci. 5, 1211 (2018).
(Invited) Three-Dimensional Porous Electrode Architecture: Impact on Electrochemistry
Authors: Takeuchi Esther S , Wang Lei , Takeuchi Kenneth J , Marschilok Amy C. 
Published: May 2020

Effective utilization of the electroactive material in thick electrodes could enable scalable batteries to be developed with higher energy densities while simultaneously reducing the overall cost of the battery. The challenges for thick electrodes include limited ion diffusion resulting in increased polarization and the inability to fully access the active material.
As part of the overall effort, the Center for Mesoscale Transport Properties is exploring alternative electrode architectures. A 3-dimensional porous electrode design was created through the deliberate incorporation of acicular carbon as part of the design strategy to enable an electrode with minimal active material agglomeration in a thick electrode (~400 µm). This design approach was explored with several active materials including high capacity conversion materials as well as layered insertion materials. In all cases, effective utilization of the active material was achieved. Further, examination of the electrode homogeneity under operando conditions was conducted using synchrotron x-ray techniques. Spatial and temporal resolution gained from the measurements provided insight into the effective electrochemical utilization.
(Invited) Enzymatic Metal Oxide Electrolyte-Gated Field-Effect Transistors for Non-Invasive Glucose Biosensor
Authors: Kim Hojoong , Chung Kwun-Bum , Kwon Jang-Yeon 
Published: May 2020

Fabrication of nano-scaled biosensors with high sensing performance is essential demand for a future biological sensing system. Detection of biomolecules is conducted in terms of change in electrical properties of the biosensor so that the consideration of semiconductor material becomes more crucial. Although a lot of attractive attentions are attempted such as utilizing silicon nanowire or carbon nanotube, studies for investigating the highly reliable and biocompatible materials still have been progressed. Metal oxide material for biosensing application has an advantages of relatively high electrical characteristics and provides environmental condition for immobilizing an enzyme. InGaZnO (IGZO) has high electron mobility and reliability which leads a high sensitivity for detecting biomolecules. Adapting field effect transistor (FET) structure is additional approach to enhance the signal response of the sensor. The fundamental principle of the FET biosensor relies on its sensitive response to the variation of electric field or potential at the sensor surface resulting from the electrical interaction between the semiconductor and glucose molecules captured at the glucose oxidase (GOx). The FET biosensor also could be effectively integrated with other application circuits through conventional photolithography technologies. In addition, electrolyte-gated FET structure, utilizing an electrolyte as a gate insulator, shows a high sensitivity to the glucose concentration originated from a large capacitance of the electrolyte.
IGZO based electrolyte-gated FET (IGZO-EGFET) biosensor is fabricated. The pH sensing is tested for predicting the biosensing performance of IGZO-EGFET. The pH sensitivity is measured as 52.5 mV/pH within 3 to 9 pH range, which is comparable to other nano material pH sensors. Immobilization of GOx on the IGZO surface is conducted via crosslinking modification with (3-aminopropyl)triethoxysilane (APTES) and glutaraldehyde treatment. Finally, the variation of glucose concentration is successfully identified on the GOx immobilized IGZO-EGFET. This study shows the IGZO-EGFET biosensor could lead to the applications of portable and real-time detecting sensor.
Layer-By-Layer Nanoassembly Of Polyelectrolites Engineered With Bioreceptors For High-Sensitivity Optical Label-Free Biosensing With Nanostructured Porous Silicon
Authors: Mariani Stefano , Robbiano Valentina , Strambini Lucanos M , Debrassi Aline , Egri Gabriela , Dähne L. , Barillaro Giuseppe 
Published: May 2020

Here we report the layer-by-layer (LbL) nanoassembly of charged polyelectrolytes engineered with bioreceptors as an effective and robust alternative to covalent biofunctionalization (e.g., organosilanization and hydrosilylation) for affinity biosensing with porous silicon (PSi) interferometers [1]. As a proof of concept demonstration, a bi-layer of positively-charged poly(allylamine hydrochloride) (PAH) and negatively-charged biotinylated poly(methacrylic acid) (b-PMAA) is assembled onto the surface of oxidized PSi interferometers for the affinity detection of streptavidin in buffer and raw saliva. The LbL nanoassembly allows a homogenous coating of the inner PSi surface, ensuring a robust anchoring of the bioreceptors and, in turn, high sensitive and selective detection of streptavidin, also in raw saliva, down to a theoretical detection limit of 600 fM. This pushes PSi based biosensors at detection limit comparable to that of state-of-the-art nanostructured photonic and plasmonic platforms for biosensing. Further, the development and employment of polymers engineered with several bioreceptors or with stronger dissociation properties (e.g. PSS) could broaden the applications LbL nano-assembly in biosensing and in biomedical applications.
[1] S. Mariani et al., Nature Communications. 2018, 9, 5256, 1-13.
(Invited) Active Molecularization of Terahertz Meta-Atoms for Bio and Medical Sensing Applications
Authors: Lee Hojin , Kim Do Hwan 
Published: May 2020

Active control of metamaterial properties is critical for advanced THz applications especially for bio and medical sensors. However, the tunability of THz properties, such as the resonance frequency and phase of the wave, remains challenging. Here, we provide a new device design for extensively tuning the resonance properties of THz metamaterials. Unlike previous approaches, the design is intended to control the electrical interconnections between the metallic unit structures of metamaterials. This strategy is referred to as the molecularization of the meta-atoms and is accomplished by placing graphene bridges between metallic unit structures whose conductivity is modulated by electrolyte gating. Because of the scalable nature of the molecularization, the resonance frequency of the terahertz metamaterials can be tuned as a function of the number of meta-atoms constituting an unit meta-molecule. At the same time, the voltage-controlled molecularization allows delicate control on the phase shift of the transmitted THz, without changing the high transmission of the materials significantly.
In this study, we propose selectively reconfigurable terahertz meta-molecules by controlling the micro-patterned ion-gel gate structures to change the conductance of graphene bridges between adjacent meta-atoms. Moreover, we experimentally verify that the proposed structures can change the resonance frequency of metamaterial device to define resonance properties from 1.40, 1.10, to 0.74 THz, by changing the metamaterial unit cell from the individual atom to dimeric and tetrameric molecules, respectively.