bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elucidating Decomposition Mechanisms of Ethylene Carbonate on Layered Cathode Material Surfaces in Lithium Ion Batteries
Authors: Qin Xueping , Shao Minhua , Balbuena Perla B 
Published: February 2020

During the charge/discharge cycling processes in lithium ion batteries (LIBs), degradation reactions of organic solvents would be inevitable at the electrode-electrolyte interface because of the instability of electrolyte components,1,2 leading to electrode degradation, capacity fade, poor cycling stability, and even safety issues. Since the reductive decomposition mechanisms of electrolytes at the anode-electrolyte interface have been extensively studied by theoretical simulations,3 it is critical to understand the interfacial reaction mechanisms at the cathode-electrolyte interface to provide more effective strategies to help design interfacial layer in LIBs, alleviating capacity fading and improving the cycle performance of batteries.
First-principles calculations were conducted to study the oxidative decomposition reactions of ethylene carbonate (EC) on the (110) surface of LiNi1/3Co1/3Mn1/3O2 (NCM333). All the possible oxidative decomposition reaction steps of EC on cathode surfaces, including H-abstraction reaction and ring-opening reactions caused by Cc-Oe and/or Ce-Oe bond cleavage, were analyzed from both thermodynamic and kinetic aspects. We found that EC decompositions are initiated by the ring-opening reaction (Cc-Oe bond cleavage) as the first step with an activation barrier of 0.57 eV and reaction energy of -0.70 eV. Afterwards, the H-abstraction reaction is quite easily to occur with an activation energy of only 0.26 eV. Figure 1 shows the reaction energies (ΔE) and activation energies (Barriers) for four possible reaction pathways as the first decomposition step for EC on NCM333 (110) surfaces. Another layered cathode material LiCoO2 (LCO) was also considered, and the similar decomposition steps were found for EC decomposition on (110) surfaces.
In a further study, lithium salt anions (PF6
-) and solvent molecules (EC) as well as Mn cations were introduced into the model. These molecules showed significant effects on the reaction pathways.

References

(1) Aurbach, D.; Gofer, Y.; Langzam, J. Journal of the Electrochemical Society
1989, 136, 3198.
(2) Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D. Energy & Environmental Science
2011, 4, 3243.
(3) Martinez de la Hoz, J. M.; Leung, K.; Balbuena, P. B. ACS Applied Materials & Interfaces
2013, 5, 13457.

Figure 1. Reaction energies (ΔE) (black filled circles) and activation energies (Barriers) (red empty circles) for four possible reaction pathways as the first decomposition step for EC on NCM333 (110) surfaces. Color code: lithium, green; carbon, brown; oxygen, red; hydrogen, white; Co, dark blue; Ni, silver gray; Mn, purple.

Figure 1
(Invited) Electrochemical Characteristics of Lithium-Ion Cells Employing Different Additives at Low Temperature
Authors: Kim Dong-Won , Kim Sang-Hyung , Park Seung Hark , Han Dong-Kwan , Kim Soojin , Kim Myung-Hoon , Park Jung Joon 
Published: February 2020

Significant attention has been paid to lithium-ion batteries (LIBs) with high energy density and excellent cycle life, because new applications such as electric vehicles (EVs) and energy storage systems (ESSs) are rapidly emerging into the market. However, current LIBs cannot satisfy the low temperature performance for further applications of EVs in cold climates. It is common that the LIBs lose most of their reversible capacity and power density as the temperature decreases below 0 oC.1,2 Therefore, improving low temperature performance has been an important subject for many researchers. In our study, we firstly try to investigate the factors that limit the low temperature performance of LIBs by using electrochemical impedance spectroscopy (EIS) analysis. Furthermore, we examine the electrochemical characteristics of LIBs with electrolyte solution containing small amounts of different low-temperature additives. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analyses have been also implemented to identify and inspect the detailed mechanism for improving the low temperature performance.
References

S.S. Zhang, K. Xu and T.R. Jow, Electrochim. Acta, 49, 1057 (2004).

K. Xu, Chem. Rev., 104, 4303 (2004).
Electrochemical Reactions at the Electrolyte–Electrode Interfaces in All-Solid-State Batteries Elucidated By Operando X-Ray Photoelectron Spectroscopy
Authors: Wu Xiaohan , El Kazzi Mario , Villevieille Claire , Novák Petr 
Published: February 2020

All-solid-state lithium ion batteries (SLiB) represent a promising battery technology thanks to the replacement of the volatile and flammable state-of-the-art liquid electrolyte by a non-flammable solid electrolyte (SE).[1] Recent progress in the development of SE with high ionic conductivity moves the battery performance, i.e. energy and power density closer to the state-of-the-art Li-ion technology.[2] Despite the significant improvement of the bulk materials properties, degradation phenomena at the electrode/electrolyte interface remain to be understood in order to ensure long-term cycling stability of the batteries. Post-mortem XPS has proved to be a powerful and appropriate technique for monitoring the chemical states of elements at the interfaces between the SE, the active materials, and conductive carbon.[3] However, it still suffers from experimental limitations to explore the full picture of the surface and interface reaction mechanisms.
We present here operando X-ray photoemission spectroscopy (XPS) as an advanced methodology to assess the interfacial (electro-) chemical reactivity between active materials (AM), conductive carbon and SE during battery cycling leading to the formation of interphases at the nanoscale which critically affects the ion transport within the SLiB. Starting from the working principles of electron spectroscopy, we derive a model to assign the observed binding energy (BE) shift to different electronic properties of the materials. This way, in addition to the observed chemical reactions in real-time, we gain further knowledge on the surface potential by analyzing the voltage dependent spectra evolution. Through an efficient experimental implementation, this method enables simultaneous monitoring of the chemical and electronic properties of the electrode-electrolyte interphases during battery operation. These fundamental knowledge will be applied and demonstrated in several case studies: i) using a mixture of amorphous (Li2S)3-P2S5 (LPS) as SE with conductive carbon, the redox reaction mechanism of the SE is fully revealed, ii) using LiCoO2 and amorphous (Li2S)3-P2S5 as SE, this methodology allows to determine precisely the oxidation potential of the SE, the interfacial reaction products as well as the cross reaction mechanisms between LCO and LPS and iii) using a mixture of In, LPS and carbon, the chemical and electrochemical reaction within a commonly used counter electrode composite is elucidated.

Reference
s
:

[1] Y. Kato, S. Hori, T. Saito, K. Suzuki, M. Hirayama, A. Mitsui, M. Yonemura, H. Iba, R. Kanno, Nature Energy, 1 (2016) 16030.
[2] N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno, M. Yonemura, T. Kamiyama, Y. Kato, S. Hama, K. Kawamoto, A. Mitsui, Nat Mater, 10 (2011) 682-686.
[3] J. Auvergniot, A. Cassel, J.-B. Ledeuil, V. Viallet, V. Seznec, R. Dedryvère, Chemistry of Materials, 29 (2017) 3883-3890.

Figure 1
(Invited) Direct Recycling of Lithium-Ion Batteries
Authors: Sloop Steven E , Xu Wei , Lerner Michael M. , Kim Joon , Lee Myongjai 
Published: February 2020

By 2025, the lithium-ion battery and disposal markets are forecast to reach $ 93 billion and $14 billion respectively. Logistics contribute to these costs, but processing takes its toll with energy intensive industrial smelting and/or hydrometallurgical technologies. As traction and storage cathode materials use less cobalt, these recycle technologies require centralized, large scale facilities to meet economic viability based upon the metal. Cobalt dilute or cobalt free applications may therefore require disposal fees, which is not helpful for circular economic sustainability for the advanced lithium-ion battery industry.
Another technological approach is necessary to address this challenge for the industry. Direct recycling has potential for cost effective recycling of lithium-ion cathodes, which is demonstrated for NMC532 and NMC622 in this work.
In the first example, NMC 532 electric vehicle grade cells were faded to 80% of their original capacity. The cells were pulverized and cathodes captured and treated and packaged. Afterwards, in a manufacturing setting, 2.2 Ah cells were built using the recycled cathode and graphite. Recycled cathode demonstrated both performance and manufacturability like new material. In side by side cycle testing, both tallied 2,500 cycles at C/10 to reach 80% of original capacity.
In the second example, starting with faded cells, NMC 622 is similarly regenerated to original capacity and rate capability. Physical characterization of NMC622 before and after processing shows the treatment reverses ageing in the surface region of the electrode particles resulting in renewed performance.
These examples show the ease and flexibility of hydrothermal and calcination processes to restore electrochemical performance to NMC cathode materials. A comparable industrial process is alumina production from bauxite, which has a world-wide production over 60,000 tons and demonstrates the scalability and low cost potential for direct recycling. The development of distributed direct recycling services reduces both logistical and production costs relative to the current approach. Direct recycling technologies provide a viable foundation for the future waste management services for the lithium-ion battery market.

Figure 1
(Invited) Evaluating the Impact of Initiation Methods on Propagating Thermal Runaway in Lithium Ion Batteries
Authors: Lamb Joshua , Torres-Castro Loraine , Karulkar Mohan , Stanley June , Grosso Christopher 
Published: February 2020

The evaluation of lithium ion battery safety has traditionally focused on the performance of single cells exposed to abusive conditions. As lithium ion batteries are fielded in increasingly large and complex systems, the system level safety performance is becoming of greater concern. Testing laboratories and battery end users have begun to consider the hazards associated with a localized thermal runaway event, a single cell or small group of cells, propagating to the bulk of a large battery system. Evaluating this propagating failure requires initiating thermal runaway of a single cell or group of cells and observing how that failure affects the surrounding system.
A major uncertainty in this testing is the impact of the initial thermal runaway initiation. The common means of initiating this testing is through abusive battery tests, but the intensity of failure may vary with the test performed and the surrounding cells potentially influenced, which in turn leads to uncertainty in the test results. This work looks at the potential impact of various failure initiating methods on the results of a propagating battery failure. Figure 1 shows a comparison of overcharge failure (left) and a nail penetration failure (right) on a 5 cell pouch cell pack. This particular result shows some change in the initial failure intensity, and the time required to initiate a failure is significantly increased in the case of the overcharge test. However, once failure is initiated the propagating behavior is similar in this case. We take a systematic look at similar affects both amongst similar construction and as the same methodology is applied across various formats and cell chemistries.
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.

Figure 1 Data showing a propagating battery failure initiated through overcharge (left) and nail penetration (right). While the failure of the initial cell is more energetic, other aspects of the propagating battery failure remain similar between each test.

Figure 1
(Invited) The Role of Variability in Failure for High Energy and High Power Batteries
Authors: Nagpure Shrikant C. , Dufek Eric J. , Tanim Tanvir R , Liaw Boryann , Dickerson Charles C 
Published: February 2020

The demand for higher power and higher energy Li-ion and Li metal batteries continues to increase. In order to meet expectations the utilization of materials and cell designs need to be optimized. The result of the need for high utilization is that small variations within a group of cells can create significant difference in performance and failure.
As part of an effort to advance the performance of Li metal batteries and specifically to increase specific energy closer to 500 Wh/kg recent work looking at the ability to more clearly understand and define the role that cell variability has on the performance of Li metal batteries has been undertaken. This work has shown that significant impact to performance arises as a set of cells, which at the beginning of life had low variability, age. Refined analysis of the electrochemical data enables key variation in Li utilization and other fade mechanisms to be clearly identified and quantified across the different cells.
Complimentary work looking at the ability to fast charge, Li-ion cells in 10 minutes or less has also begun. This presentation will discuss the analysis methodology, key similarities in identifying the role of variability and how a more refined understanding can significantly impact the technology development pathway.
Towards First-Principles Design of Battery Components for Current and Next-Generation Li-Ion Batteries
Authors: Viswanathan Venkatasubramanian 
Published: February 2020

Complete electrification of transportation and aviation requires more energy-dense batteries and requires a much more rapid design iteration loop.[1,2] Computation and data will play a crucial role towards achieving this goal. The design of Li-ion batteries components - anode, electrolyte and cathode require simulation capabilities at varying length and time scales. Here, we will discuss our group's progress in using first-principles modeling and data-driven methods for designing liquid electrolytes, solid electrolytes and cathodes. We highlight the importance of open source methods, especially in the context of phase-field modeling for describing Li metal based anodes. We will show the crucial role played by a tight integration between atomic scale and continuum scale simulations to identify material targets for various use-cases. We believe that a vertically integrated modeling approach is necessary to enable rapid development of next-generation Li-ion batteries to power electric semitrucks and aircrafts.
[1] S. Sripad, V. Viswanathan, J. Electrochem. Soc. 164 (11), E3635-E3646.
[2] S. Sripad, V. Viswanathan, ACS Energy Lett. 2 (7), 1669-1673.
(Invited) Rational Design of Battery Cathode Materials
Authors: Cho Kyeongjae 
Published: February 2020

We will discuss about applying ‘materials by design’ and validation experimental research on high capacity cathode materials for Li and Na ion batteries (LIB and NIB). Using the first-principles density functional theory (DFT) method, we have designed electrode materials for battery cathodes, and subsequently performed experimental studies to validate the material designs. Through an integrated material design - experiment research, we have developed highly efficient cathode materials for NIB. [1] Furthermore, using the DFT based stability analysis of Li(Ni,Mn,Co)O2 (NMC) cathode materials, the underlying mechanisms of stability change in Ni-rich NMC cathodes are elucidated over the range of 30 – 100 % Ni concentration in metal composition. [2-6] Surface analysis of Ni-rich NMC has also provided insights on the degradation mechanisms (both chemical and mechanical) facilitating to develop a design strategy to improve the stability of Ni-rich NMC over 80% Ni contents. [7]
This work was also supported by the International Energy Joint R & D Program (No. 20168510011350) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Ministry of Knowledge Economy, Korean government.
[1] D. Kim, M. Cho, K. Cho, “Rational Design of Na(Li1/3Mn2/3)O-2 Operated by Anionic Redox Reactions for Advanced Sodium-Ion Batteries,” Adv Mater 29(33), 1701788 (2017).
[2] Chaoping Liang, F, Kong, R. Longo, Santosh KC, Jeom-Soo Kim, SangHoon Jeon, SuAn Choi, K. Cho, “Unraveling the Origin of Instability in Ni-Rich LiNi1−2xCoxMnxO2 (NCM) Cathode Materials,” The Journal of Physical Chemistry C 120(12), 6383–6393 (Mar. 31, 2016)
[3] R. C. Longo, F. Kong, C. Liang, D. -H. Yeon, J. Yoon, J. -H. Park, S. -G. Doo and K. Cho, “Transition Metal Ordering Optimization for High-Reversible Capacity Positive Electrode Materials in the Li-Ni-Co-Mn Pseudoquaternary System,” Journal of Physical Chemistry C 120(16), 8540-8549 (Apr. 28, 2016).
[4] F. Kong, C. Liang, L. C. Roberto, D.-H. Yeon, Y. Zheng, J.-H. Park, S.-G. Doo and K. Cho, “Conflicting Roles of Anion Doping on the Electrochemical Performances of Li-ion Battery Cathode Materials”, Chem. Mater. 28(19), 6942–6952 (Oct. 11, 2016)
[5] Chaoping Liang, Roberto C. Longo, Fantai Kong, Chenxi Zhang, Yifan Nie, Yongping Zheng, Jeom-Soo Kim, SangHoon Jeon, SuAn Choi, and K. Cho, “Obstacles toward unity efficiency of LiNi1-2xCoxMnxO2 (x=0~1/3) (NCM) cathode materials: Insights from ab initio calculations” Journal of Power Source 340, 217-228 (2017).
[6] C. Liang, F. Kong, R. Longo, C. Zhang, Y. Nie, Y. Zheng, K. Cho, “Site-dependent multicomponent doping strategy for Ni-rich LiNi1-2yCoyMnyO2 (y=1/12) cathode materials for Li-ion batteries,” J. Mater. Chem. A 5(48), 25303-25313 (Dec. 2017).
[7] C. Liang, R. Longo, F. Kong, C. Zhang, Y. Nie, Y. Zheng, K. Cho, “Ab initio Study on Surface Segregation and Anisotropy of Ni-rich LiNi1-2yCoyMnyO2 (NCM) (y ≤ 0.1) Cathodes,” ACS Appl. Mater. Inter. (2018).
(Invited) Recent Advances in the DFT-Based Search of Cathode Materials for Ca Batteries
Authors: Torres Arturo , Casals Jose Luis , Luque Javier , Tortajada José , Arroyo-de Dompablo M. Elena 
Published: February 2020

In the last years, concerns on Li availability have prompted the search for suitable alternatives to rechargeable Li-ion batteries. Batteries based on multivalent charge carriers (Mn+) can exhibit advantages in terms of energy density since for a certain amount of M carriers the capacity is doubled (n=2) or tripled (n=3) when compared to single valent carriers like Li+ or Na+. Calcium is an attractive candidate due to its low cost, natural abundance and low reduction potential. At this very early stage of the Ca-batteries technology, the quest for a high specific energy cathode material is an active field. The general goal of our work is the identification of materials able to function as positive electrode in Ca batteries.
DFT is a unique tool to quickly screen a variety of structures and compositions to identify potential cathode materials for this novel technology. The general strategy is firstly to calculate average voltage and volume changes associated to the Ca insertion reaction. Further, DFT theory could be applied to gather additional information regarding electronic and ionic conductivities, crystal structure of intercalated phases and precise voltage-composition-curves at various temperatures. In this communication, we will present a survey of recent results for oxides, silicates and sulphides as cathode for Ca batteries. Special attention is given to the calculation and analysis of Ca migration pathways using the NEB method. In good agreement with parallel experimental investigations [1-3], we found that the low ionic mobility is the main handicap for the insertion/deinsertion of Ca ions in most structures. Yet, for some materials, Ca intercalation is predicted at low C rates.
Acknowledgments: Authors are grateful for financial support from European Union H2020-FETOPEN funded project CARBAT-766617.
References;
[1]. M.E. Arroyo-de Dompablo, C. Krich, J. Nava-Avendaño, M.R. Palacin, F. Barde. Phys. Chem. Chem. Phys. 18 (2016) 19966.
[2]. M.E. Arroyo-de Dompablo, C. Krich, J. Nava-Avendaño, N. Biskup, M.R. Palacin, F. Barde. Chem. Mater. 28 (2016) 6886.
[3]. D. Tchitchekova, A. Ponrouch, R. Verrelli, T. Broux, C. Frontera, A. Sorrentino, F. Barde, N. Biskup, M.E. Arroyo-de Dompablo, M.R. Palacin. Chem. Mater. 30 (2018) 847.
Vertically Aligned and Tree-like Carbon Nanostructured for Electrode of Electrochemical Capacitors
Authors: Ghosh Monalisa , Mohan Rao G 
Published: February 2020

Vertically aligned and tree-like nanostructures of carbon are grown by using plasma enhanced chemical vapour deposition (PECVD) method using electron cyclotron resonance (ECR) plasma system. These nanostructures consist of a multiwalled carbon nanotube which is aligned perpendicular to the surface of the substrate with carbon films attached to it like “branches” of a tree giving the structure a tree like appearance. The thin film of these nanostructures is deposited in a ECR plasma system on a nickel seed layer with a microwave power of 500 W using acetylene and hydrogen gas in 2:1 ratios as the source gases, at a working pressure of 7x10-4 mbar in presence of a negative substrate bias of 200 V 1. As the material with its vertical alignment and tree-like morphology has a very high exposed surface area, this material was speculated to act as a high-performance electrode of electrochemical capacitors (EC) or supercapacitors. The unique three-dimensional morphology of the material gives a high surface area with less areal footprint of the material.
The electrochemical performance of the material as electrode of EC has been studied by depositing the material of thickness 1 μm on circular stainless-steel substrates of diameter 12 mm (area 1.13 cm2). 1 M Na2SO4 solution in deionised water is used as the electrolyte for the EC with absorbed glass mat as the separator between the two nanostructured electrodes. The entire assembly is done inside Swagelok type cell for testing the electrochemical performance. The EC showed a specific capacity of 920 μF/cm2 (9.2 mF/cc) at a scan rate 0.1 V/s which is higher than the reported values for vertically aligned carbon nanotube.2–4 A rectangular cyclic voltammetry curve is observed even at a voltage of 1 V/s. The results indicate that this material is a promising candidate for electrode material of supercapacitor.

References

M. Ghosh and G. M. Rao, Carbon
133, 239–248 (2018).

B. Hsia, J. Marschewski, S. Wang, J Bin In, C. Carraro, D. Poulikakos, C. P. Grigoropoulos and R. Maboudian Nanotechnology, 25, 055401(9pp) (2014)

T. Chen, H. Peng, M. Durstock, and L. Dai, Sci. Rep., 4, 1–7 (2014).

C. L. Pint et al., Carbon N. Y., 49, 4890–4897 (2011)

Figure 1