bluuebunny/crossref_metadata_2025_split huggingface dataset:
Anodic Layer Growth on 1050 and 2024 Aluminium Alloys in Presence of Etidronic Acid : Changes in Morphology and Structure
Authors: Jérémy Daval , Moutarlier Virginie , Viennet Rémy , Ricq Laurence , Hihn Jean-Yves 
Published: July 2022

Anodic layer growth during anodization is a well-known phenomenon, used to increase the thickness of the natural layer present on the surface of metals for corrosion resistance. In the case of pure aluminum and its alloys, the porous oxide layer leading to a regular structures with nanopores arrangements, which provides interesting corrosion resistance and mechanical performances. The most frequent electrolytes (sulfuric, oxalid or phosphoric acid) induce low current/voltage at direct or pulsed modes to elaborate the oxide layer according to the different electrochemical windows. If the anodic oxide film elaborated in the first moment is soluble into the electrolyte, a porous structure take place with pores oriented perpendicular to the metal surface. The formation of the barrier layer occurs at the interface between the metal and the porous layer, but is thin enough to allow a continuous ionic flow which lead to a continuous film growth.
The present work deals with aluminum anodization in etidronic acid (HEDP) at very high voltages for aluminum 1050 and 2024 alloys. It appears that the oxide layer growth, studied by XRD and SEM pictures of cross section obtained by ionic polishing, differs clearly for the reason that pores formations not only starts from the barrier layer, but also at different locations such as the oxide layer/electrolyte interface. The final result consist in an oxide layer with excellent functional properties.
(Invited) Bare and Modified Cu(111) Electrocatalysts: Interfacial Structure and Reactivity
Authors: Auer Andrea , Bandarenka Aliaksandr S. , Hörmann Nicolas , Andersen Mie , Reuter Karsten , Kunze-Liebhäuser Julia 
Published: July 2022

A very important parameter for the electrocatalytic performance of a material is its potential of zero free charge (pzfc). For Cu(111) at pH 13 it was identified at −0.73 VSHE in the apparent double layer region. It shifts by (88±4) mV to more positive potentials per decreasing pH unit.1 At the pzfc, Cu(111) starts to restructure. At higher potentials, full reconstruction and electric field dependent OH adsorption occur, causing a remarkable decrease in the atomic density of the first Cu layer.1 It is this restructuring that enables Cu(111) to efficiently oxidize CO and to reduce water. Therefore, knowledge of the surface structure and the position of the pzfc is of paramount importance for the understanding of copper’s catalytic properties and for the rational design of electrocatalysts.
CO is a key intermediate in the electro-oxidation of energy carrying fuels and known to act as a catalyst poison. Single-crystal Cu(111) model catalysts can efficiently electro-oxidize CO in alkaline media,2 where strong surface structural changes are observed under reaction conditions with electrochemical scanning tunneling microscopy (EC-STM). Supported by first-principles microkinetic modelling, we have shown that the concomitant presence of high-energy undercoordinated Cu structures at the surface is a prerequisite for the high activity.
In water electrolyzers, it is possible to produce H2 in the course of the hydrogen evolution reaction (HER), which was studied with Ni(OH)2 and Co(OH)2 modified Cu(111) electrodes in alkaline media.
3 Strong morphological changes upon adatom modification lead to a significant HER rate enhancement. Intriguingly, this is induced through a decrease of the electric field strength negative of the pzfc. This implies an easier reorganization of the interfacial water molecules facilitating charge transfer through the double layer, and thus enhancing the efficiency of electrocatalytic reactions. The tendency of Cu(111) to restructure is found to dominate its electrochemical properties. The structural changes of the electrode surface are intimately related to the electric field at the solid/liquid interface and to its electrocatalytic activity, in general.
References:
[1] A. Auer, X. Ding, A. S. Bandarenka, J. Kunze-Liebhäuser, J. Phys. Chem. C 125 (2021) 5020.
[2] A. Auer, M. Andersen, E.M. Wernig, N.G. Hörmann, N. Buller, K. Reuter, J. Kunze-Liebhäuser, Nature Catal. 3 (2020) 797.
[3] A. Auer, F.J. Sarabia, D. Winkler, C. Griesser, V. Climent, J.M. Feliu, J. Kunze-Liebhäuser, ACS Catal. 11 (2021) 10324.

Figure 1
(Invited) Lithium Metal Nucleation and Growth on Conductive Substrates— a Multi-Scale Understanding from Micro, Meso, to Macro-Scales
Authors: Liaw Boryann (Bor Yann) 
Published: July 2022

Repetitive lithium (Li) metal deposition and stripping on conductive substrates such as copper is a critical process involved in the rechargeable Li batteries for high energy applications. Most of the time, the reversibility of this deposition and stripping process by electrochemical methods is of paramount importance for long life performance of these batteries. Solid electrolyte interphase (SEI) formation and the dendritic formation of Li whiskers are often cited as the challenges in achieving a uniform, reversible Li deposition and stripping in the process, rendering a short life duration of these batteries for practical applications. The fundamental question of how Li metal nucleates and grows on the conductive substrate has not been well understood until some recent experiments and in situ, operando observations [1,2] began to shed light on this process to offer some clues how to control the morphology of the Li deposition and stripping process.
Here, a collection of experimental evidence and molecular dynamics simulations are presented to provide some insight of this seemingly straightforward process of elemental metal deposition. An explanation to peel off the mystery of the Li nucleation and growth from the atomic level to the micro (<20 nm), meso (20-100 nm), and the macro-scale (>100 nm) is offered to provide some guidance of the control needed to regulate the morphology. Success to demonstrate some highly dense and reversible Li deposition and stripping is shown.
References:

Fang, B. Lu, G. Pawar, M. Zhang, D. Cheng, S. Chen, M. Ceja, J.-M. Doux, M. Cai, B. Liaw, Y. S. Meng, “Pressure-tailored highly-reversible lithium metal electrode for rechargeable lithium batteries.” Nat. Energy 6 (2021) 987–994. https://doi.org/10.1038/s41560-021-00917-3

Wang, G. Pawar, Y. Li, X. Ren, M. Zhang, B. Lu, A. Banerjee, P. Liu, E. J. Dufek, J-G. Zhang, J. Xiao, J. Liu, Y. S. Meng, B. Liaw, “Glassy Li metal anode for high-performance rechargeable Li batteries.” Nat. Mater. 19 (2020) 1339–1345. https://doi.org/10.1038/s41563-020-0729-1
Cyclic Carbonate-Based, Single-Ion Conducting Polymer Electrolytes for Li-Ion Batteries: Battery Performance
Authors: Park Habin , Engler Anthony , Liu Nian , Kohl Paul 
Published: July 2022

Solid polymer electrolytes (SPEs) are a pathway for safe, and high energy and power lithium batteries due to their thermal stability and low vapor pressure. Although polymers can be flexible and dimensional stability, it is lithium dendritic suppression can be a challenge for any electrolyte. Conventional SPEs have both mobile cations and anions, which migrate and cause concentration polarization. The low transference number for lithium ions in an electrolyte contributes lithium concentration gradients causing concentration polarization and lithium dendrites [1,2]. Single-ion conducting SPEs have been reported to demonstrate lithium ion only conduction in the electrolyte as well as retain their high mechanical stability during cycling. However, their low ionic conductivity is due to stationary phase of the tethered anion in the polymer matrix and cation-anion complexation [3].
In this study, a cyclic carbonate neutral moiety was included in the SPE to help dissociate the lithium cation from the tethered anion matrix to increase the ionic conductivity and help form the solid electrolyte interphase (SEI) layer. The cyclic carbonate unit in the SPE is similar to the cyclic carbonate solvent in a conventional lithium ion battery and could participate in the solvation of the lithium cation in the SPE. The cyclic carbonate monomer in the SPE can participate in SEI-forming electrochemical reactions on the electrode surface and suppress undesirable side reactions and lithium dendritic growth. Satisfactory level of rate and cycling performance was achieved with the novel neutral monomers in the single-ion conducting SPEs.
[1] H. Zhang, C. Li, M. Piszcz, E. Coya, T. Rojo, L.M. Rodriguez-Martinez, M. Armand, Z. Zhou, Chem. Soc. Rev. 2017, 46, 797-815.
[2] F. Ahmed, I. Choi, M.M. Rahman, H. Jang, T. Ryu, S. Yoon, L. Jin, Y. Jin, W. Kim, ACS Appl. Mater. Interfaces
2019, 11, 34930-34938.
[3] D.-M. Shin, J.E. Bachman, M.K. Taylor, J. Kamcev, J.G. Park, M.E. Ziebel, E. Velasquez, N.N. Jarenwattananon, G.K. Sethi, Y. Cui, J.R. Long, Adv. Mater.
2020, 32, 1905771.
(Invited, Digital Presentation) Pushing the Limits of High Nickel NMC Cathodes
Authors: Whittingham Stan , PEI BEN , Buyuker Isik , Lee Krystal , Xin Fengxia , Zhou Hui 
Published: July 2022

Lithium-ion batteries now dominate electrochemical energy storage for vehicle propulsion and grid storage in addition to portable electronics. In 2022, they celebrate their 50th anniversary, and yet still achieve only 25% of their theoretical energy density. The dominant anode and cathode today are graphitic carbon and the layered NMC oxides, LI[NiMnCoAl]O2. Both need improving. Most of the carbon in the anode must go, and the NMCs need pushing to their limit and at the same time eliminating cobalt. I will today discuss the challenges faced as we push the limits of the NMCs to their limits, > 80% lithium cycling, and Ni>0.8 and Co <<0.1. The higher the Ni content the lower the charging voltage needed for a given cycling capacity, but the greater its surface and bulk reactivity. The issues discussed will include 1stcycle loss [1], high rate capability [2], cathode stability [3], and surface/bulk reactivity and the impact of surface/bulk modification [4,5] and the micron-size single crystals vs meatballs on these [6]. This work is being supported by DOE-EERE-BMR-Battery500 consortium.
[1]. Hui Zhou, Fengxia Xin, Ben Pei, M. Stanley Whittingham, “What Limits the Capacity of Layered Oxide Cathodes in Lithium Batteries?”, ACS Energy Lett. 2019, 4: 1902−1906.
[2]. Chunmei Ban, Zheng Li, Zhuangchun Wu, Melanie J. Kirkham, Le Chen, Yoon Seok Jung, E. Andrew Payzant, Yanfa Yan, M. Stanley Whittingham, and Anne C. Dillon “Extremely Durable High-Rate Capability of a LiNi0.4Mn0.4Co0.2O2 Cathode Enabled by Single–Wall Carbon Nanotubes”, Advanced Energy Materials, 2011, 1: 58-62.
[3]. Hyung-Joo Noh, Sungjune Youn, Chong Seung Yoon, Yang-Kook Sun “Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = ¼ 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries”, J. Power Sources, 2013, 233: 121-130.
[4]. Fengxia Xin, Hui Zhou, Yanxu Zong, Mateusz Zuba, Yan Chen, Natasha A. Chernova, Jianming Bai, Ben Pei, Anshika Goel, Jatinkumar Rana, Feng Wang, Ke An, Louis F. J. Piper, Guangwen Zhou, and M. Stanley Whittingham, “What is the Role of Nb in Nickel-Rich Layered Oxide Cathodes for Lithium-Ion Batteries?”, ACS Energy Letters, 2021, 6: 1377-1382.
[5]. Ben Pei, Hui Zhou, Anshika Goel, Mateusz Zuba, Hao Liu, Fengxia Xin, and M. Stanley Whittingham, “Al Substitution for Mn during Co-Precipitation Boosts the Electrochemical Performance of LiNi0.8Mn0.1Co0.1O2”, J. Electrochemical Society, 2021, 68: 050532.
[6]. Yujing Bi, Jinhui Tao, Yuqin Wu, Linze Li, Yaobin Xu, Enyuan Hu, Bingbin Wu, Jiangtao Hu, Chongmin Wang, JiGuang Zhang, Yue Qi and Jie Xiao, “Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode”, Science, 2020, 370: 1313-1317.
(Invited) Advanced Characterizations of Interfaces in Solid-State Batteries
Authors: Yao Yan 
Published: July 2022

The complex origins of solid-state battery failure call for multidimensional diagnostics utilizing a combination of tools that can quantify the void and dendrite formation, identify the chemical and mechanical natures of the Li dendrites and electrolyte decomposition products. However, there is lack of tools that connect multiple techniques with desirable length scale, resolution and sensitivity for characterizing solid-state batteries. We will present out effort in developing an air-free vessel with an in-situ cell test platform connecting FIB-SEM tomography, ToF-SIMS, and in-SEM nanoindentation for structural, chemical, and mechanical characterizations of solid-state Li batteries. We fabricated solid-state micro-cells with electrochemical performance on par with their bulk-type counterparts. Electrochemical tests with precise temperature control, external pressure, and pressure monitoring of thin solid-state cells were demonstrated with structural, chemical and mechanical characterizations.
This work was supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Vehicle Technologies Program under Contract DE-EE0008864.
Application of Tetraethylsulfamide (TES) As a Cathode Additive in Cylindrical Cells
Authors: Ma Xiaowei , Wood Bryan D. , Way Brian 
Published: July 2022

Recently, sulfonamides have been shown to be promising electrolyte components due to their high chemical and electrochemical stability in lithium batteries [1, 2]. The electrolyte stability becomes critical when applying high voltage and/or utilizing Ni-rich layered oxides in high energy density lithium-ion batteries. Another approach to successful Ni-rich cathode performance is to develop a stable and effective cathode electrolyte interphase (CEI). Given the success of sultones and sulfates in this regard [3, 4], it is hypothesized that nitrogen analogs, like sulfonamides, could be tailored to provide a similar benefit. Indeed, Yim et al. [5, 6] have shown that N,N,N’,N’-tetraethylsulfamide (TES) forms a CEI on NMC811 that imparts high voltage cycling stability and less cathode corrosion. Our earlier studies of TES with Ni-rich NCA also formed a favorable CEI and these results are the topic of this presentation.
Herein, we examine the performance of 0 - 4 wt.% TES in our commercially available, high power INR18650-P28A. These cells contain a composite SiO/graphite anode in addition to a Ni-rich cathode. As shown in Fig 1, TES significantly decreased the impedance of the cathode interface after conditioning compared to the control electrolyte. Thereafter, cells containing up to 2%TES show improved capacity retention during long-term high-rate cycling (+1C/-80W). Part of this success was due to a suppression of resistance growth during cycling by TES. Fast charge cycling (+3C/-2C), however, was moderately impaired with increased TES. Considering the largely reduced impedance of the cathode, fast-charge performance may have suffered due to anode rate limitations. These results will be discussed as well as gas generation, storage performance, and additional rate and cycling tests.
[1] Shuting Feng, Mingjun Huang, Jessica R. Lamb, Wenxu Zhang, Ryoichi Tatara, Yirui Zhang, Yun Guang Zhu, Collin F. Perkinson, Jeremiah A. Johnson, Yang Shao-Horn. Chem, 5, 2630-2641 (2019)
[2] Weijiang Xue, Mingjun Huang, Yutao Li, Yun Guang Zhu, Rui Gao, Xianghui Xiao, Wenxu Zhang, Sipei Li, Guiyin Xu, Yang Yu, Peng Li, Jeffrey Lopez, Daiwei Yu, Yanhao Dong, Weiwei Fan, Zhe Shi, Rui Xiong, Cheng-Jun Sun, Inhui Hwang, Wah-Keat Lee, Yang Shao-Horn, Jeremiah A. Johnson, Ju Li. Nature Energy, 6, 495-505 (2021)
[3] Koji Abe, Manuel Colera, Kei Shimamoto, Masahide Kondo, Kazuhiro Miyoshi. Journal of Electrochemical Society, 161 (6) A863-A870 (2014)
[4] Jian Xia, N. N. Sinha, L. P. Chen, J. R. Dahn. Journal of Electrochemical Society, 161 (3) A264-A274 (2014)
[5] Kwangeun Jung, Taeeun Yim. Journal of Alloys and Compounds, 834,155155 (2020)
[6] Ji Won Kim, Kwangeun Jung, Taeeun Yim. Journal of Mater. Sci & Tech. 86, 70-76 (2021)

Figure 1
Design Framework for Cobalt and Ni-Free High-Capacity Lithium-Ion Cathodes
Authors: Nanda Jagjit 
Published: July 2022

Growing demand for Lithium-ion batteries for electric transportation and grid-scale storage will inevitably put resource constraints in terms of availability of key critical battery materials such as cobalt, nickel, lithium, and graphite. Specifically limited global reserve of elements such as cobalt and nickel will lead to severe supply chain issues driving the cost and contributing to market uncertainty. Given such scenario, there has been a significant effort in the global research community to develop high performance battery materials derived from relatively earth abundant elements. The talk will highlight ongoing research at PI’s Laboratory and collaborators on developing cobalt-free disorder rock salt (DRX) cathodes for next generation Li-ion. Most practical Li-ion cathode materials have well-ordered structures (e.g., spinel, layered, olivine), while the DRX compounds do not require any cation ordering. Instead, Li transport is achieved by percolation through a cation-disordered within the dense crystalline rock salt structure. Since DRX compounds do not necessitate a layered structure, they do not necessarily require cobalt metal and can be synthesized from an extremely wide variety of common metals, including Ti, Mn, Ni, Al, Nb, Mo, V, Zr, etc. Therefore, such class of materials provides plenty of chemical options for cathode design for Li-ion. Another key enabling aspect for this class of cathodes is the role of fluorine in stabilizing the high voltage oxygen redox and capacity retention. The talk will focus specifically on synthesis and structural design of Li-Mn-Ti-OF based DRX compositions and pathways for improving high voltage redox and stability.
This work performed at Oak Ridge National Laboratory is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, under the Applied Battery Materials Program, of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725
(Digital Presentation) Temperature Rise during High-Power Pulses of Lithium-Ion Batteries
Authors: Knehr Kevin , Kubal Joseph , Dees Dennis , Nelson Paul , Ahmed Shabbir 
Published: July 2022

Lithium-ion batteries currently dominate the light-duty electric vehicle (EV) market due to their high energy density, low self-discharge, and high efficiency. Because of these advantages, Li-ion batteries are now being explored for next-generation EV applications like heavy trucks and aerial vehicles. The new applications present design challenges somewhat different from light-duty, road vehicles. For instance, aerial EVs during take-off and landing or heavy trucks on lengthy inclines/declines require high power (or regenerative) pulses for >1 minute. These long-duration, high power pulses may lead to significant temperature rise that could damage the battery and/or produce unsafe conditions resulting in thermal runaway. Accurate estimations of the temperature rise during these pulses are important for initial studies focused on assessing the validity of Li-ion batteries in these and other applications.
This work starts by demonstrating how the accuracy of approximating the temperature rise using Joule heating – i.e., I2R, where I is the applied current and R is the electrochemical resistance – decays considerably for high power pulses. A 3-D thermal-electrochemical model of an NMC532-Graphite pouch cell is then used to explain the causes of the deviation. It is shown that a combination of transport in the electrolyte and self-heating cause variations in the resistance during the pulse, which invalidate the Joule heating approximation. Insights from these results are used to develop a correlation for the temperature rise during high power pulses. The correlation provides an improved estimation of the temperature using minimal experimental data for the area specific resistance of the cell.
Development of a Programmable Rastering Open-Source Electrodeposition System
Authors: Avery Hayden , Jurkovic Jacob , Marara Iragi , Salaripoor Hamidreza , Bruce David Robert 
Published: July 2022

A prototype rasterizable electroplating system constructed entirely of open-source systems and off-the-shelf electronic components has been developed. The system as proposed can be broken down into separate movement and electroplating systems. The movement system consists of a Creality Ender 3 3D-Printer which has been modified to support the electroplating system. This electroplating system was built using an Arduino microcontroller that controls the voltage and current of the system. The system polarization can be controlled potentiostatically or galvanostatically in an operating window of 0 to 5V with currents up to 300 mA and a stability of 2% accuracy.
The results presented will be a demonstration of the system operation in an electrolytic capacity, with simple water splitting in a bicarbonate solution chosen to examine the controls and system readings when electrodes are moved geometrically throughout a simple two electrode cell with unequal electrode shapes. A discussion of the set-up process for this system follows to elaborate on the challenges of translating STL file decoding to the path the printer must follow, which is then further sliced and translated to Gcode. Limitations to the Gcode generation and further modifications to allow for cross-communication between the Arduino and Ender control systems are discussed, highlighting the limitations of these economic yet powerful system builds.