bluuebunny/crossref_metadata_2025_split huggingface dataset:
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: December 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.
The Role of Hydrated Alumina Layer on the Incorporation of Electrolyte Species in Anodizing of Aluminum
Authors: Habazaki Hiroki , Takano Tatsuyuki , Kowalski Damian , Kitano Sho , Aoki Yoshitaka 
Published: December 2020

Hydration treatment of aluminum is often used for corrosion protection of aluminum alloys and for the formation of dielectric alumina layer in aluminum electrolytic capacitors. Hydrated alumina layer is usually formed by immersing aluminum with and without a porous anodic alumina layer in hot water. The hydrated alumina layer plays an important role in enhancing the corrosion resistance and forming crystalline γ’-alumina in subsequent barrier-type anodic film growth by anodizing. However, the properties of the hydrated layer are not yet well understood. In this study, we examined the influence of anion incorporation properties into the barrier-type anodic alumina films through the hydrated alumina layer, which was formed in hot water.
High purity (99.99%) aluminum plate was used in this study. After electropolishing in a HClO4–ethanol mixed solution below 283 K, a hydrated alumina layer was formed by immersing the electropolished aluminum in hot water (95ºC) for 10 min. The resultant hydrated layer consists of two layers, comprising a flake-like outer porous layer and a relatively dense inner layer. The thickness of the hydrated layer was ~430 nm. Then the aluminum with the hydrated layer was anodized in boric acid and tungstate electrolytes to grow the barrier-type anodic films. When the boric acid electrolyte was used, boron species were incorporated into the outer part of the barrier-type anodic films through the hydrated alumina layer. In contrast, no incorporation of tungsten species into the barrier-type anodic film through the hydrated layer occurred in the tungstate electrolyte. Phosphate anions are known to be incorporated into the 70% of the film thickness in the anodic amorphous alumina film, but in the present study, phosphate anions were not incorporated into the barrier-type anodic films through the hydrated layer. It is likely from the GDOES elemental depth profile analysis suggests that the inner hydrated layer becomes a barrier for the incorporation of tungsten and phosphorus species. Thus, apparently, the inner hydrated alumina layer has cation-selective permeation properties so that anion incorporation is limited. In boric acid electrolyte, the acid dissociation is limited, and non-charged boric acid species can be penetrated through the hydrated layer.
Adhesive Property of Aluminum Oxide Formed By High Temperature Anodizing
Authors: Nakajima Daiki , Saito Sohei , Oya Yoshiyuki , Suzuki Shinobu 
Published: December 2020

Aluminum and its alloys have been widely used various situations because of their light weight, specific strength, heat conductivity. Surface treatment can impart corrosion protection, hardness, coating film adhesion and others to aluminum. Anodizing is one of the most important surface finishing processes of aluminum. In recent years, technology to use multimaterials has been attracting attention to achieve the production of energy-efficient automobiles. In such activities, adhesive bonding is increasingly used in automobile manufacturing. However, the reliability and strength of the joint surface is very important to use adhesive bonding for vehicle such as car, aircraft and motorcycle. Herein, we demonstrate the fabrication of high adhesive aluminum surface via high temperature anodizing process.
High-purity aluminum specimens (99.99 wt%, 300 µm thick) were ultrasonically degreased in acetone for 10 min. These specimens were immersed in a oxalic acid solution (0.3 M), and then were anodized at a constant current density using a direct-current power supply. After anodizing, the specimens were quickly removed from the electrolyte solution and then washed with distilled water. The surface nanomorphology of the anodized specimens was examined by field emission scanning electron microscopy (FE-SEM). The adhesion property of anodized specimen was measured by tape peel test using 90 degree peel test machine.
Figure 1 shows the surface appearance of the specimens covered with a) typical anodic oxide formed by low-temperature anodizing and b) anodic oxide formed by high-temperature anodizing. Anodic oxide formed by high-temperature anodizing had an irregular shape numerous pores due to the chemical dissolution of anodic oxide. These photographs were taken after tape peel test. On the typical anodic oxide, the tape was easily peeled off and no adhesive remained on the surface. On the other hand, the tape adhesive remained on the irregular anodic oxide covered surface fabricated by high temperature anodizing and the strong tape peel strength was measured. High-temperature anodizing causes the intense chemical dissolution. Thus, the anodic oxide which had wide-pore outer layer and intricate inner layer was formed on the aluminum surface by high-temperature anodizing. Adhesive layer of tape might be able to penetrate such anodic oxide. Therefore, the strong peel strength by the anchoring effect was measured on the surface. Although the adhesive mechanism has not been clear in detail, this surface treatment technique has a potential for the fabrication of composite material which is consist of aluminum and another material．

Figure 1
Compositional Variations in Nanotubes/Nanopores Formed on Fe(100), Fe(110) and Fe(111) Single Crystals
Authors: Kowalski Damian 
Published: December 2020

Anodizing is a high voltage electrochemical conversion process that forms barrier-type oxide layers or self-organized nanoporous/nanotubular structures. So far, alumina-like nanopores and titania-like nanotubes could be successfully synthesized on many valve metals and alloys. Recently, anodizing become possible for base metals such as polycrystalline iron and its alloys. The challenge in anodizing of iron lies in the proper control of corrosion/passivity, which can be successfully realized in organic electrolytes containing small amount of water. 1-3 Anodic nanotubes and anodic nanopores may be formed on polycrystalline iron depending on electrochemical conditions adjusted in anodizing protocol (Fig. 1). The polycrystalline iron is typically composed of the grains having the size of 2-10 mm. The kinetics of metal oxidation as well as oxygen evolution reaction, which is typically observed upon iron anodizing, may depend on the iron facet exposed to the electrolyte. In order to evaluate the dependence of the crystallographic orientation on the formed anodic film structure we investigated anodizing process on iron single crystals, namely Fe(100), Fe(110) and Fe(111). The compositional differences for porous films formed on single crystals were analyzed by means of by high resolution electron microscopy EDS elemental mapping.
References:

H. Habazaki, Y. Konno, Y. Aoki, P. Skeldon and G. E. Thompson, Journal of Physical Chemistry C, 2010, 114, 18853-18859.

Y. Konno, E. Tsuji, P. Skeldon, G. E. Thompson and H. Habazaki, J. Solid State Electrochem., 2012, 16, 3887-3896.

K. Shahzad, D. Kowalski, C. Y. Zhu, Y. Aoki and H. Habazaki, ChemElectroChem, 2018, 5, 610-618.

Figure 1 Bright field TEM micrograph for FIB cross-section of anodic iron formed at 100V in ethylene glycol electrolyte containing 1.5M H2O and 0.1M NH4F.

Figure 1
Electrochemical Properties of High Nickel NMCA Materials
Authors: PEI BEN , Zhou Hui , Whittingham Stan 
Published: December 2020

Lithium nickel manganese cobalt oxides (NMC) with high nickel composition are considered as the most promising candidates for the next-generation cathode because of their high reversible capacities (180−250 mAh g−1), high voltage window, and reasonable rate capability. However, the highly reactive Ni4+ ions tend to cause unfavorable side reactions with the electrolyte, which leads to an electrochemical inactive NiO-type rock-salt phase associated with oxygen loss on the surface at the highly delithiated state, degrading the structure of materials. Furthermore, the dramatic lattice contraction in a rather short period after charging to high voltage (>4V) causes cracks along the grain boundaries, which damages the particle integrity, delivering a gradual fading of the reversible capacity and thermal stability during cycling.
Aluminum substitution is an effective strategy to stabilize the lattice structure and suppress oxygen release due to the Al-O bonds are stronger compared to other transition metal-oxygen bonds. To maximum the impact of the Al, a uniform substitution in the host structure is essential. Here we report an in-situ Al substitution strategy for NMC811, which leads to robust layered structures, reducing the phase transition and side reactions on the surface of high nickel NMC materials at the highly delithiated state. This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy, through the Advanced Battery Materials Research Program (Battery500 Consortium)
High-Performance Cobalt-Free Nickel-Rich Layered Li[Ni0.9Mn0.1]O2 Cathode Materials
Authors: Aishova Assylzat , Nam Gyeong Won , Sun Yang-Kook 
Published: December 2020

With growing demands for low-cost, large-format lithium-ion batteries mainly for electric vehicles (EVs) and energy storage system (ESS), escalating price and unsustainable supply of cobalt have become increasingly acute.1 Moreover, owing to the toxic nature and an increasing concern for child labor used in ore mining, significant research is being devoted to decrease the share or completely removing cobalt from the current cathode families, particularly in high-capacity Ni-rich layered cathodes which have sufficiently high potential for commercialization.2-5

This study involves a systematic investigation on the Ni-rich Li[Ni0.9Co0.1-xMnx]O2 (x = 0, 0.05, and 0.1) layered cathodes by variation of the Mn to Co content. Remarkably, Co-free Li[Ni0.9Mn0.1]O2 (NM90) exhibits outstanding mechanical and microstructural stability resulted in excellent cycling performance, which outperformed its Co-containing Li[Ni0.9Co0.1]O2 and Li[Ni0.9Co0.05Mn0.05]O2 counterparts. Alongside observations of high voltage and high-temperature stability, Co-free NM90 demonstrate substantially higher capacity retention, increasing the attractiveness of this material for practical application.
To elucidate the impact of the Mn content in Ni-rich cathodes, the characterization techniques such as in-situ XRD, TEM and micro-compression analysis as well as electrochemical measurements have conducted and provided valuable information regarding the intrinsic properties of individual cathode components and their effects on electrochemical performance of the cathode materials.

References

Y.-K. Sun, D. J. Lee, Y. J. Lee, Z. Chen and S.-T. Myung, ACS Appl. Mater. Interfaces
2013, 5, 11434.

U.‐H. Kim, D.‐W. Jun, K.‐J. Park, Q. Zhang, P. Kaghazchi, D. Aurbach, D. T. Major, G. Goobes, M. Dixit, N. Leifer, C. M. Wang, P. Yan, D. Ahn, K.‐H. Kim, C. S. Yoon and Y.‐K. Sun, Energy Environ. Sci.
2018, 11, 1271.

K.-J. Park, M.-J. Choi, F. Maglia, S.-J. Kim, K.-H. Kim, C. S. Yoon and Y.-K. Sun, Adv. Energy Mater.
2018, 8, 1703612.

U.‐H. Kim, H.‐H. Ryu, J.‐H. Kim, R. Mücke, P. Kaghazchi, C. S. Yoon and Y.‐K. Sun, Adv. Energy Mater.
2019, 9, 1803902.

U.‐H. Kim, L.-Y. Kuo, P. Kaghazchi, C.S. Yoon and Y.-K. Sun, ACS Energy Lett.
2019, 4, 576.
(Invited) Probing the Ultrafast Molecular Transport Kinetics in Microscopic/Second Scale
Authors: Wen Bohua , Deng Zhi , Tsai Ping-chun , Lebens-Higgins Zachary , Piper Louis F.J. , Ong Shyue Ping , Chiang Yet-Ming 
Published: December 2020

Today, the electrical power supplies pose increasingly stringent requirements on battery package, for example, ultrafast vehicles charging algorithms and high current power supplies. To enable the optimal combination of energy and power capability, it is essential to understand kinetic barriers at all applicable length scales and time scales. On the length scale, we developed single electrode particles of ~25 µm size of a few nAh and adopted it to zoom in the transport of the molecules within the solid|liquid interface, excluding the complicated factors from typical composite electrode microstructures. The particle level electrodynamic measurements conducted in varied electrolyte compositions, reveal the anion group effects in charge transport, which leads to a significantly higher materials utilization during fast charge/discharge in both the single-particle measurements and on macroscopic composite electrodes. Furthermore, molecular dynamics (MD) simulations identify the preferred solvation structures of the liquid electrolytes, and density functional theory (DFT) calculations of their binding energies reveal the origin of the anion group effect. The anion dependence and the solvation lead to the fast kinetics at the interface. On the time scale, we probed the ultrafast transport algorithm with high-frequency modulation. A modulated DC pulse charging and discharging with high-frequency waveforms (up to ~ MHz) are performed to investigate the interfacial transport. This study reveals a possible mechanism by which ion transport kinetics in a lithium-ion battery are responsive to megahertz frequency excitation. Such algorithms are aiming to improve active material utilization as well as cycle life dramatically.
This work was supported as part of the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DESC0012583.
A Dilatometric Study of Graphite Electrodes during Cycling with X-Ray Computed Tomography
Authors: Michael Harry , Brett Dan , Shearing Paul R. 
Published: December 2020

Since the 1970s, electrochemical dilatometry (ECD) has been used to investigate the dilation of layered host materials due to the intercalation of guest ions, atoms or molecules , but to date has not been extensively applied to Li-ion batteries (LiBs) [1][2]. Understanding how commonly adopted anodes dilate and degrade in LiBs using ECD can be of critical value in improving the battery. Cathode materials also undergo volume changes during cycling, the extent of which is dependent on their stoichiometry and structure. However, the influence of cathode material dilation and contraction on battery performance, and overall cell dilation is often neglected [3].
Graphite is the mostly widely used commercial anode material in LiBs because of its high coulombic efficiency and cycling performance. However, prolonged cycling of LiBs has a deleterious effect on the graphite electrode’s durability. The present study uses correlative ECD to reveal the thickness changes of the electrode during cycling, alongside X-ray Computed Tomography (X-ray CT). X-ray CT provides additional visual corroborative evidence of the morphological changes that occur during cycling and explains changes in dilatometric measurements. X-ray CT is also used to acquire images of cycled and uncycled graphite electrodes for simulations exploring how continuous dilation and contraction impact electrode porosity and tortuosity.
To date, there is no research to our knowledge combining in-situ ECD with X-ray CT and image-based modelling. In this presentation, the structural changes that graphite undergoes during dilation and contraction will be explored, and the consequences that continuous dilation and contraction has on morphological properties, namely porosity and tortuosity will be explained.

References:

Sauerteig, D., Ivanov, S., Reinshagen, H. & Bund, A. Reversible and irreversible dilation of lithium-ion battery electrodes investigated by in-situ dilatometry. J. Power Sources
342, 939–946 (2017).

Winter, M., Wrodnigg, G. H., Besenhard, J. O., Biberacher, W. & Novák, P. Dilatometric Investigations of Graphite Electrodes in Nonaqueous Lithium Battery Electrolytes. J. Electrochem. Soc.
147, 2427 (2000).

Persson, J. V, Danzer, M. A., Bauer, M., Wachtler, M. & St, H. Understanding the dilation and dilation relaxation behavior of. 317, 93–102 (2016).

Figure 1
Three-Dimensional Imaging and Interface Analysis of Battery Materials Via Plasma FIB-SEM
Authors: Zhang Minghao , Liu Zhao , Shojaee S. Ali , Winiarski Bartlomiej , Doux Jean-Marie , Lemmens Herman , Meng Shirley Shirley 
Published: December 2020

In the past decades, the rapid growth of electric vehicles and consumer electronics market leads battery technology to attract significant attention. In order to further advance battery technology, in-depth understanding on the electrode and interface structure of battery materials are essential. Focused ion beam – scanning electron microscope is an analytical method combines ion beam for materials processing and electron column for imaging. It enables both 2D interface analysis and 3D imaging capability as well as multimodal information collection, which is an effective analytical approach for battery structure analysis.
To date, conventional Ga+ FIB-SEM has been widely employed for battery materials development including interface/interphase characterization, 3D quantification and simulation analysis. However, Ga+ FIB materials removal efficiency limits its capability to access representative area and volume in some battery materials systems, e.g. electrode with tens of micron particle size. In addition, the reactive property of Ga+ ion with alkali metals, e.g. Li metal, results in the complex experimental procedure to limit the Ga+
contamination during FIB-SEM characterization.
Recently, the emerging Plasma FIB-SEM (PFIB-SEM) technology has been developed with different ion source and high removal efficiency. It promises great potential for battery materials characterization, due to accessing representative 2D area and 3D volume via 40 times faster (than Ga+ system) milling rate as well as enabling Ga+ free sample preparation on advanced battery system with alkali metal electrode through non-reactive ion source (Xe+ and Ar+ ion). In this presentation, PFIB-SEM has been used to perform 2D interfacial structure analysis and 3D imaging on different battery systems. First, to evaluate the performance of plasma ions processing with Ga+ reactive battery system, lithium metal was selected for the study. Furthermore, the interfacial structure between Li-metal and sulfide based solid electrolyte in all solid-state battery system was investigated. In order to demonstrate the capability of accessing large representative 3D volume through PFIB-SEM, the microstructure of thick NMC 811 cathode (>100 µm field of view with > 70 µm thickness) was selected for 3D reconstruction and quantification. The microstructural characteristics extracted from representative 3D volume helps the understanding of correlation between electrode microstructural evolution and performance deterioration.
The success demonstration of PFIB-SEM opens up exciting opportunities for exploring both current and future generation advanced battery technologies, which is expected to become a critical analytical approach for battery development.
Ultrahigh Power and Energy Density in Partially Ordered Lithium-Ion Cathode Materials
Authors: Ji Huiwen , Cai Zijian , Wu Jinpeng , LIU Jue , Kwon Deok-Hwang , Urban Alexander , Ceder Gerbrand 
Published: December 2020

Conventional Li-ion cathodes are stoichiometric intercalation materials (e.g., LiCoO2, NCM, LiMn2O4). We will present here our efforts to make high capacity, high rate materials based on the earth abundant Mn redox center by partially disordering a cation-excess spinel. In an ordered spinel, the two-phase reaction that occurs at low voltage (~2.7 V) is not only intrinsically slow, but also detrimental to the structural stability because of the large difference in lattice constant between the two end points (cubic and tetragonal phases)1. Recently, Li-excess cation disordered rock salt materials have shown remarkable cycling performance-large capacities and high energy densities2,3. We applied the Li-excess strategy to the spinel structure to synthesize metal-excess, Li-excess partially-disordered spinels. Disorder is induced to remove the two-phase region, and metal excess and Li-excess is used to create high mobility Li-ions and enablement of O-redox. Two partially disordered spinels with compositions between spinel and rocksalt stoichiometry are presented4: Li1.68Mn1.6O3.7F0.3 (LMOF03) and Li1.68Mn1.6O3.7F0.3 (LMOF06). A remarkably high specific energy density greater than 1,100 Wh kg–1 (and capacity >360 mA h g–1) can be achieved in LMOF03, with nearly half of the capacity coming from oxygen redox. On top of that, facilitated by the beneficial spinel-like cation order and the elimination of two-phase reactions, both LMOF03 and LMOF06 show a very high rate capability with a capacity larger than 100 mA h g-1 at 20 A g-1. Our strategy of combining Li-excess and cation over-stoichiometry in a spinel structure to enable high energy and power at the same time can also be applied to other materials.
1 Thackeray, M. M., David, W. I. F., Bruce, P. G. & Goodenough, J. B. Lithium insertion into manganese spinels. Materials Research Bulletin
18, 461-472 (1983).
2 Lee, J. et al. Reversible Mn 2+/Mn 4+ double redox in lithium-excess cathode materials. Nature
556, 185 (2018).
3 Lee, J. et al. Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries. Science
343, 519-522 (2014).
4 Ji, H. et al. Ultrahigh power and energy density in partially ordered lithium-ion cathode materials. Nature Energy, doi:10.1038/s41560-020-0573-1 (2020).