bluuebunny/crossref_metadata_2025_split huggingface dataset:
Non-Isothermal Aging of Lithium-Ion Cells
Authors: Bloom Ira , Thomas Edward V , Christophersen Jon P , Robertson David C , Walker Lee K , Ho Chinh , Battaglia Vince 
Published: February 2020

Lithium-ion batteries are rapidly being adopted for transportation applications, ranging from hybrid- to full-electric vehicles. To assure that the automotive battery can meet the demands of these applications, the US Advanced Battery Consortium has established test manuals and performance targets for each application [1-3]. These manuals use accelerated tests to gather needed performance degradation information in a limited amount of time. Models are then developed from these data that relate performance decline to the magnitude and duration of the stress. Isothermal aging stresses the battery under a simple set of conditions and can be used to elucidate the underlying degradation mechanisms. It is then generally assumed that a cumulative degradation model of aging under non-isothermal conditions would be a linear combination of the isothermal results. However, this approach may not directly predict the non-isothermal behavior. A model based on degradation rates may be a better predictor. In theory, integrating the rate-based model over the temperature path can then express the cumulative degradation. The results of this investigation will be discussed.
The work at Argonne National Laboratory was performed under the auspices of the U.S Department of Energy (DOE), Office of Vehicle Technologies, under Contract No. DE-AC02-06CH11357. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. The efforts at Idaho National Laboratory and at Lawrence Berkeley National Laboratory were performed under Contract Numbers DE-AC07-05ID14517 and DE-AC03-76SF00098, respectively.
This article issue has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (Argonne). Argonne, a DOE Office of Science Laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up, nonexclusive, irrevocable, worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government.

References

FreedomCAR Battery Test Manual for Power-Assist Hybrid Electric Vehicles, DOE/ID-11069, October 2003.

Battery Test Manual for Plug-In Hybrid Electric Vehicles, Rev. 3, INL/EXT-14-32849, September 2014.

Battery Test Manual for Electric Vehicles, INL/EXT-15-34184, Rev. 3, June 2015
Mechanistic Study of Parasitic Reactions on Cathodes of Lithium-Ion Batteries
Authors: Chen Zonghai , Zeng Xiaoqiao , Ma Tianyuan , Amine Khalil 
Published: February 2020

The side reactions between the change electrode materials, delithiated cathodes or lithiated anodes, significantly contributes to the continuous and irreversible consumption of accessible lithium during the normal charge/discharge cycling, leading to a degradation on electrochemical performance of lithium-ion batteries. Understanding these side reactions, parasitic reactions, is crucial for the development of robust algorithm for predicting the remaining life of a specific battery and for the development of functional materials for long-life lithium-ion batteries.
Figure 1a shows a home-built high precision electrochemical testing system used to study the kinetics of parasitic reactions on LiNi0.6Mn0.2Co0.2O2. Figure 1b schematically shows the principle of the measurement. The working electrode was held at a specific potential using the source meter, maintaining a constant state-of-the-charge (SOC) for the working electrode. During this process, the electron obtained from the environment by the oxidation of the solvent, will be electrochemically collected by the external circuit. The measured leakage current is proportional to the reaction rate of parasitic (side) reactions between the working electrode and the electrolyte. Hence, the static leakage current can be used as a quantitative indicator for the reaction rate of the side reactions. Figure 1c shows a typical current relaxation curve collected, an exponential decay function was used to extract the static current (y0in Figure 1C), and to (1) minimize the impact of the high frequency noise, and (2) to get rid of the potential impact of slow intercalation/deintercalation reaction.
In this work, the reaction mechanisms between delithiated cathodes and the non-aqueous electrolyte will be discussed.

Figure 1
Investigation on Electrochemical Properties and Degradation Mechanism of Cylindrical-Type Li-Ion Rechargeable Battery without Deconstruction
Authors: Kobayashi Hironori , Kuratani Kentaro , Koike Shinji , Saito Yoshiyasu 
Published: February 2020

Recently Li-ion rechargeable battery (LIB) has been widely used as power source of not only portable device but also electric vehicle (EV). For LIBs in EVs, a long life of 10 years or more is required. Therefore, a great deal of effort has been made to develop the prediction method of life of LIB for EV. We have already started to measure battery performance for LIBs being used in practical EVs and developed the prediction method of battery life based on the degradation mechanism of the active materials in the batteries.

In this paper, we investigated battery performance of cylindrical-type cells with Sn-containing negative electrode. Sn-containing materials are promising negative electrode materials for LIB because of large theoretical capacity compared with that of conventional carbon materials. Both general cycle and storage tests were carried out for each 25 cells at 298 K and 318 K, and the capacity, DC resistivity and power density of these cells were checked every fixed period. We also applied the X-ray CT method to cells as an analytical technique without deconstruction, and confirmed visually to detect the internal structure in the cells definitely.

In the presentation, we will discuss the degradation mechanism of the cells using Sn-containing negative electrode mainly by the combination of the prediction method of battery life and the X-ray CT method without deconstruction of cells.

Acknowledgement
This work was partly supported by the New Energy and Industrial Technology Development Organization (NEDO).
Novel Diagnostic Methods Via Instrumented Lithium Batteries
Authors: Bhagat Rohit , Fleming Joe , McTurk Euan , Seth Sampan , Dashwood Richard , Greenwood David , Ferrari Stefania 
Published: February 2020

Defect propagation and material degradation affect both the performance and safety of energy storage systems. Both processes may accompany operation over time, be nucleated during manufacturing, or be initiated rapidly by external stimuli. This raises particular concerns in lithium-ion cell technologies, where the consequences of faults can be dramatic. However, to date, we have limited capability to detect and/or predict these critical lifetime- and reliability-determining events, especially during operation under real-world operating conditions.
In this paper we present our work related to embedding sensors within and around commercially available pouch and cylindrical format cells. The types of sensors include reference electrodes for measuring half cell voltages during operation, optical fibres to measure mechanically and thermally induced strain, and magnetoresistive sensors to measure the local magnetic field resulting from the flow of charge. Embedding of these sensors is not trivial as the performance of the cell must be unaffected by the modifications. Furthermore, the embedded sensors must survive the cells internal environment. Methodologies for embedding sensors in pouch and cylindrical cells are discussed.
These instrumented cells collectively provide a powerful suite of in-situ and in-operando diagnostics for assessing performance, detecting defect propagation and materials degradation. These diagnostic methods are of great academic interest allowing ageing and failure mechanisms to be studied in greater detail. Furthermore, such diagnostic methods would also be useful in industry allowing systems reliant on lithium battery technology to be characterised in relation to battery operation. Here we present examples of the use of instrumented cells to understand the changes occurring within the cells when operated outside manufacturers’ guidelines and under abuse conditions. Data showing progression of failure is also presented.
Diagnostic Examination of NCM523//Graphite Cells Cycled at High Voltages
Authors: Abraham Daniel P , Gilbert James A 
Published: February 2020

High energy materials are needed to increase the energy density of Li-ion batteries for vehicular applications. Layered-oxides are promising high energy positive-electrode materials; however, the performance of cells containing these oxides degrades faster when cycled to high potentials (> 4.3 V). In order to understand the origin of this performance loss, we conducted extensive tests with 2032-type coin cells and reference electrode (RE) cells; the results of these tests will be reported during this presentation.
The coin cells in this study contain 1.6 cm2 area Li1.03(Ni0.5Co0.2Mn0.3)0.97O2-based (NCM523) positive and a graphite-based negative electrode (Gr); the electrolyte is 1.2M LiPF6 in EC:EMC (3:7 w/w) electrolyte (Gen 2). The reference electrode cells contain 20.3 cm2 area NCM523-positive and Gr-negative electrodes, two Celgard 2325 separators enveloping a LixSn RE, and a Li-metal RE external to the electrode sandwich. Cell cycling includes formation cycles followed by aging cycles; pulse-power and AC impedance measurements are made periodically throughout the cycling.
The Li-metal RE provides information on the positive and negative electrode potentials during full cell cycling; such information cannot be obtained from the coin cell data. For example, during cell formation, when the full cell is cycled between 3.0 and 4.4 V, the positive electrode cycles between 3.67 and 4.46 V vs. Li/Li+ and the negative electrode cycles between 0.67 and 0.06 V vs. Li/Li+. The electrode cycling potential ranges change during cell aging. Furthermore, electrode impedances measured with the LixSn RE also change during aging. We will highlight the reasons for these changes during the presentation.
In addition to the electrochemistry results we will discuss data obtained by various diagnostic techniques that include the following: Scanning electron microscopy, Raman spectroscopy, and X-ray diffraction. Our mechanistic understanding of the capacity fade and impedance rise of the NCM523//Gr cells will be discussed through these various data.
(Invited) Investigation of the Reaction & Degradation Mechanism of Iron Based Cathodes for Sodium-Ion Batteries Using X-Ray Absorption and Time-Resolved X-Ray Diffraction Techniques
Authors: Ali Ghulam , Kim Dong-Hyun , Lee Ji-Hoon , Chung Kyung Yoon 
Published: February 2020

Because of the growing level of energy consumption, numerous efforts have been made to develop high performance rechargeable batteries to use for large scale applications such as electrical energy storage systems (ESS). Lithium ion batteries have been the most popular and widely used batteries in portable devices like cell phones, laptops, etc. However, it has some constraints to be used for large scale applications as the cost for the raw materials for lithium is expensive. There have been ongoing studies searching for alternative shuttle ions and sodium can be one of the possible substitutes since it is more abundant and cheaper. The development of high performance cathode materials is required for the realization of sodium-ion batteries (SIBs) as the reduction potential of sodium is lower and its ionic radius is larger compare to lithium. Because of larger ionic radius, the de/intercalation of sodium causes to large volume contraction/expansion of the host materials which could affect the rate capability and long cycle life. The structural analysis during electrochemical reaction can provide better insight to understand the material’s behavior. Furthermore, thermal analysis is one of the critical issues for the electrodes and causes to the failure of the battery system.
Here, we report the synthesis, electrochemical properties and investigate the reaction mechanism of iron fluoride hydrate and iron phosphate cathodes for SIBs. The crystal structure of iron fluoride hydrate is refined and the results show pyrochlore structure (with space group of Fd3m) with hydrate contents residing in zigzag positions. Thermal stability of the as prepared iron fluoride hydrate is determined using thermogravimetric analysis coupled with temperature-dependent TR-XRD. A nanocomposite of iron fluoride hydrate encapsulated within reduced graphene oxide sheets is prepared as cathode for the high performance SIBs. The nanocomposite delivers a high discharge capacity of ~260 mAh/g at current density of 0.05 C (1C=220 mAh/g) and it retains a discharge capacity of 230 mAh/g over 100 cycles, demonstrating a good cycle stability. The ex situ TEM and XANES have employed to determine the reaction mechanism. The surface of the olivine iron phosphate is modified with a polymer (thiophene) to improve the electrochemical performance. The coating with thiophene not only increases the electrical conductivity but also prevent the degradation of the material. The coated electrode exhibits high electrochemical performance and delivers a discharge capacity of 142 mAh g-1 with capacity retention of 94% after 100 cycles. The reaction mechanism of the coated electrode has been investigated using x-ray absorption spectroscopy. Thermal analysis of the cycled electrode is conducted using temperature-dependent TR-XRD.
Coupling Surface Imaging, FIB, and Spectroscopies to Understand Silicon Anodes Lithiation and Ageing Mechanisms
Authors: Bordes Arnaud , De Vito Eric , Haon Cédric , Montani Alexandre , Boulineau Adrien , Marcus Philippe 
Published: February 2020

To follow growing energy demand of new devices, batteries energy density needs to be improved. Silicon-based anode is a serious option since it offers a specific capacity almost ten times higher than carbonaceous materials. Even so silicon anodes suffer from a drastic capacity fading making it unusable after few cycles. A fine understanding of the lithiation mechanism of silicon could participate to the elaboration of more robust architectures.
In this work1, composite silicon electrodes have been electrochemically cycled vs Li. After a transfer from a glove box to a ToF-SIMS by using an air-tight vessel, chemical mapping of the inside of silicon grains can be done by achieving an in-situFIB cut.
The first lithiation has been extensively studied. By stopping lithiation at different stages it is possible to follow the evolution of the core-shell structure (ie LiSi alloy shell and pure Si core) as shown in fig.1. This method also permits to observe the Si particles, considering their position within the depth of the electrode. To complete this study, cross analysis with Auger spectrometer, SEM and TEM have been performed, allowing to quantify Li presence in the LixSi alloy and better understand the pure Si core morphology. At the end, a complete mechanism for silicon particles is proposed.
In a following step, Si electrodes have been observed after 3, 5 and 10 cycles (limited capacity of 1000 mAh.g-1) in both lithiated and delithiated states. After three cycles the core-shell structure is still visible in lithiated state. After 10 cycles the presence of Si particles containing lithium at the end of the charge are observed and associated to particle getting out of the conductive grid and trapping lithium. This phenomena are detrimental to battery lifespan and participate in the failure of limited cycling strategies.

(1) Bordes, A.; De Vito, E.; Haon, C.; Boulineau, A.; Montani, A.; Marcus, P., Multiscale Investigation of Silicon Anode Li Insertion Mechanisms by Time-of-Flight Secondary Ion Mass Spectrometer Imaging Performed on an in Situ Focused Ion Beam Cross Section. Chem. Mater. 2016.

Figure 1
Polyoxometalate Modified Biomass Carbon Composites for Supercapacitor Electrodes
Authors: Genovese Matthew , Lian Keryn 
Published: February 2020

Polyoxometalates (POMs), nanoscale transition metal-oxide clusters, have emerged as promising building blocks for the fabrication of pseudocapacitive electrodes.[i] These POM clusters undergo fast reversible electron transfer reactions and have multiple stable redox states, ideal characteristics for energy storage applications.[ii] In order to leverage these properties for use in electrochemical capacitor (EC) electrodes, these POM clusters must be immobilized on a stable carbon substrate to create a composite electrode. There is synergy in this combination as the POMs contribute faradaic redox processes, while the carbon provides stability, high conductivity, and electrochemical double layer capacitive (EDLC) contributions.
Porous carbon derived from biomass is an excellent potential substrate for these POM-carbon composites owing to its low cost, simple synthesis procedure, and high specific surface area. Here, we will report on our synthesis of porous carbon substrates derived from pine cone biomass via a two-stage carbonization and chemical activation procedure. These pine cone carbon samples are highly porous with specific surface areas over 2500 m2 g-1. In a sulfuric acid electrolyte, the high surface area of these samples results in a double layer capacitance of 265 F g-1. In order to further enhance this already large capacitance, the biomass carbons were modified with Keggin POM clusters, PMo12O40
3- and PW12O40
3- via a single step chemisorption.
We have discovered that the intrinsic porosity and surface conditions of the pine cone biomass carbon are particularly well suited to the immobilization of Keggin POMs. Additionally, by adjusting the activation conditions, the carbon porosity can be tuned to further enhance POM chemisorption. The result is biomass carbon hybrids with exceptionally high loading of POM clusters. The redox activity of these immobilized POMs leads to significantly enhanced area and volume specific capacitance compared to the bare carbon substrate (Figure 1). In this talk, we will present the full characterization of the POM-biomass carbon hybrids as well as discuss the activation conditions and resulting substrate porosity necessary for superior POM adsorption. The POM chemistry that results in the optimal pseudocapacitive performance will also be presented and discussed.

[i] M. Genovese, K. Lian. Current Opinion in Solid State and Materials Science. 19 (2015) 126-127
[ii] B.B Xu, L. Xu, G.G. Gao, W.H. Guo, S.P. Liu. J. Colloid Interface Sci. 330 (2009) 408

Figure 1
(Invited) Ultracapacitive Energy Storage Using 2D Nanomaterials Under Extreme Conditions
Authors: Park Ho Seok 
Published: February 2020

With increasing demand for high performance energy storage devices, the feasibility of reliable and functional energy storage devices that well operates under extreme conditions is of prime importance for expanding applicative fields as well as for understanding materials’ intrinsic and extrinsic properties and device physics.1-4 In this talk, I will introduce the control in the physical structure and chemical composition of 2D nanomaterials for ultracapacitive energy storage devices under limited circumstances, where conditions are classified into thermodynamic (e.g. pressure, volume and temperature) and kinetic (e.g. high rate and frequency) variables.1-10 In addition, a fundamental foundation via in-situ spectroscopic techniques will be presented to understand charge storage phenomenon of new materials and devices occurring on a nanoscale under various circumstances.8-10

Keywords: Supercapacitor, 2D nanomaterials, Graphene, Pseudocapacitors, Flexible energy storage.
Ref.
[1] Ho Seok Park*, et al.
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, 2016, 26, 903–910.
[2] Ho Seok Park*, et al.
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[3] Ho Seok Park*, et al.
ACS Nano.
, 2015, 9, 8569-8577.
[4] Ho Seok Park*, et al.
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, 2015, 25(7) 1053-1062.
[5] Ho Seok Park*, et al.
ACS Nano
, 2011, 5 (9) 7205-7213.
[6] Ho Seok Park*, et al.
ACS Nano
, 2011, 5 (6) 5167–5174.
[7] Ho Seok Park*, et al.
ChemSusChem
, 2014, 7(4) 1094-1101.
[8] Ho Seok Park*, et al.
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, 2015, 15, 576-586.
[9] Ho Seok Park*, et al.
Nano. Lett.
, 2015, 15 (4), 2269-2277.
[10] Ho Seok Park*, et al.
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Chemically Deposited NiCo2O4 Thin Films for High-Performance Supercapacitors
Authors: Deokate Ramesh J. , Kalubrame Ramchandra S. , Lokhande Chandrakant D 
Published: February 2020

Changes in climatic conditions resulting from the consumption of fossil fuels and their limited availability have affected the global ecology and economy. The shift towards a more sustainable energy economy has illustrated the need for the development of low cost and environmentally friendly energy storage systems. Supercapacitors, also known as ultracapacitors or electrochemical capacitors, warrant broad important applications in electric vehicles and mobile power sources due to the unique combination of their properties, such as rapid charge–discharge behavior and higher specific power density than batteries and fuel cells while possessing higher energy densities than conventional double layer capacitors.
NiCo2O4-based materials have been intensively investigated for pseudocapacitors due to their high theoretical specific capacitance, good chemical and thermal stability, natural abundance, environmental benignity and low cost. In the present work, Nickel cobalt oxide (NiCo2O4) thin films have been systematically prepared using spray pyrolysis method for its application in supercapacitors. Briefly, we prepared two different aqueous solutions of 0.1 M nickel chloride and cobalt chloride by dissolving in de-ionized water (DIW), respectively. In the spray pyrolysis process, aqueous solutions of nickel and cobalt precursor mixed with volume ratio 1:2 were sprayed over the FTO substrates maintained at various temperatures in the form of mist using air-blast spray pyrolysis unit. The sprayed mist undergoes thermal decomposition to form the NiCo2O4 thin films. The electrochemical performance of the NiCo2O4 thin film was measured in a 2M KOH electrolyte with potential window 0 to 0.5 V. Galvanostatic charge– discharge (GCD) studies were also carried out.
The field-emission scanning electron microscopy (FE-SEM) image shown in Fig. 1, reveal that compact and uniform thin films of cubic nickel cobaltite with particle size 10-20 nm has been obtained by the oxidation of Ni and Co precursors. Moreover, it is observed that nanostructured NiCo2O4 thin film deposited at 350 0C exhibit the best charge storage property with high specific capacitance of 752 F g−1 and excellent cycle stability over 1000 cycles. The high specific capacitance, remarkable rate capability and excellent cycling stability of the composites mean that they show promise for application in supercapacitors.

Figure 1