bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Phase Evolution and Interfacial Strain in Electrode Materials for Batteries
Authors: Su Dong 
Published: May 2020

Advanced (scanning) transmission electron microscopy ((S)TEM) techniques have been intensively applied to study the materials for energy storage. With/Combining different TEM techniques, including in-situ TEM and diffraction, HAADF-STEM, and STEM-electron energy-loss spectroscopy, researchers are able to probe local structural and chemical information of electrode materials, at a resolution of nanoscale. This talk will focus on my recent work on using in-situ and analytical TEM to characterize the conversion-reaction oxide material (Fe3O4) for electrode of lithium ion batteries [1-3]. The dynamical process of the redox reaction of Fe3O4 revealed by in-situ TEM may help us to understand how reaction pathways affect the batteries’ kinetic properties.

Reference
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[1] He K. et al., Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron eicroscopy, Nature Communications, 7,11441 (2016)
[2] Hwang S. et al., Strain coupling of conversion-type Fe3O4 thin film for lithium ion battery, Angewandte Chemie, 56,7813, (2017)
[3] Li J. et al. Phase evolution of conversion-type electrode for lithium ion batteries, Nature Communications, 10,2224 (2019)
Investigation of Electron-Beam Induced Damage in Lithium-Ion Batteries
Authors: Jaberi Ali , Zaghib Karim , Gauvin Raynald 
Published: May 2020

Lithium-ion batteries are extensively used to transform chemical energy into the electrical energy and vice versa. These batteries are inevitably the best candidates for portable devices such as mobile phones, laptops and specially in the fast-growing market of electrical automobiles. The performance of these batteries is strongly connected to the microstructure of their electrodes. Thus, improvement of lithium-ion batteries requires an accurate structural investigation of their electrodes which is achievable by using electron microscopes.
However, the electron microscopes may damage the specimen during the investigation process. Once the beam electrons penetrate into the material, the columbic force of nucleus and electrons can scatter the beam electrons. When beam electrons undergo high angle scattering events, the law of conservation of momentum required momentum transfer to the atoms in the sample. In cases where the transferred energy is large enough to overcome a barrier called displacement energy (Ed), the atom can be displaced from its original lattice site. This displacement of atoms is called knock-on displacement, a significant source of electron beam damage. As a light element, Lithium has very small displacement barrier which makes the lithium base electrodes vulnerable to the high energy beam of electron microscopes.
In this study, we use a Density Functional Theory (DFT) based method called Nudged Elastic Band (NEB) to calculate the displacement energies. These values were then applied to the conservation of momentum to find the threshold displacement energy which is the beam energy that creates the knock-on damage inside the material during the electron microscopic investigation. Finding the safe electron beam energy range opens a new door for more accurate structural characterization of lithium compounds as a step for further improvement of lithium ion batteries.
Chemistry, Microstructure, and Interphases of Magnesium Metal Anodes Captured Via Cryogenic Electron Microscopy
Authors: Long Daniel , McClary Scott , Hahn Nathan T , Zavadil Kevin R , Watt John , Jungjohann Katherine L 
Published: May 2020

Lithium-ion batteries are an important component in mobile electronics; however, their modest energy density makes them less than ideal for use in all-electric vehicles or localized grid residential/commercial energy storage. Multivalent-ion batteries (MIBs), including Mg2+, are promising high-energy density technologies that are cheaper and more abundant than lithium. Realizing the high theoretical energy density of MIBs requires the native multivalent-ion metal to be used as the anodic electrode, where densely controlled metal plating and stripping has yet to be achieved. The mechanisms governing plating/stripping of MIBs and the resulting microstructural impact on the battery performance must be understood before MIBs can be employed commercially. Understanding the role that the solid electrolyte interface has on multivalent-ion metal plating/stripping may lead to solutions for controlling reversible anodic cycling.
Recent advances in cryogenic electron microscopy(cryo-EM) preparation have allowed for scanning transmission electron microscopy (STEM) investigation of intact solid/liquid interfaces and electron-beam-sensitive materials. Here we present results of our chemical and microstructural investigation of plated and stripped Mg2+ anodes, collected with cryo-FIB preparation, cryo-transfer, and cryo-STEM. Details will be presented on the anode porosity, grain orientation maps, chemical maps from the electrode/electrolyte interfaces, and high-resolution structural imaging of the electrode interfaces.
This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. 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. DOE’s National Nuclear Security Administration under contract DE-NA-0003525. The views expressed in the article do not necessarily represent the views of the U.S. DOE or the United States Government.
In-situ and Operando Characterization of Battery Materials using X-rays
Authors: Sommariva Marco , Dadivanyan Natalia , Nenert Gwilherm , Fransen Martijn , Degen Thomas , Masiello Fabio , Bao Zhaohui , Wang Lin , Speakman Scott , Hawkridge Mike , Gateshki Milen 
Published: May 2020

X-ray diffraction, scattering and imaging are powerful tools for the study of battery materials [1, 2]. In this work we describe several X-ray methods, which can provide a wealth of information about new materials used in battery applications. By using X-ray diffraction (XRD) it is possible to identify the different crystallographic phases, and with the Rietveld method [3] it is possible to refine the crystallographic structures of the different materials and quantify the amount of each phase in the bulk material. It is also possible to perform in situ and operando XRD measurements of the complete battery cells. This can be done either in reflection or in transmission geometry [4-6]. In order to perform the measurements in transmission geometry, radiation with higher energy is required, e.g. Mo or Ag X-ray anodes. A newly developed Malvern Panalytical X-ray detector (GaliPIX3D) allows for shorter measurement time and/or better data quality thanks to the higher efficiency of the CdTe sensor material [7]. In addition, the short-range structure of crystalline, nano-crystalline and amorphous materials can be studied with the Pair Distribution Function method (PDF), based on a total scattering approach. Also for this technique, hard X-ray radiation (Mo or Ag anodes) is required. Imaging is also a very useful technique, enabling detailed view of the interior structure of the battery in a non-destructive way. All X-ray scattering and imaging experiments can be performed on a single X-ray instrument, such as a Malvern Panalytical Empyrean multipurpose diffractometer.
[1] E. Talaie et al., Energy & Environmental Science 8, 2512-2523 (2015)
[2] Z. Liu et al., Chemistry of Materials 26(8), 2513-2521 (2014).
[3] H.M. Rietveld, J. Appl. Cryst. 2, 65 (1969).
[4] I. Buchberger et al., Journal of The Electrochemical Society 162(14), A2737-A2746 (2015).
[5] N. Sharma et al., ChemSusChem, 8, 2826-2853 (2015).
[6] E. Talaie et al., Chemistry of Materials, DOI: 10.1021/acs.chemmater.6b02726 (2016).
[7] G. Confalonieri et al., Powder Diffraction Journal, 30(2), Supp. 1, S65 (2015).
Impact of Iron Elusion on the Capacity Degradation of FeF3 –Two-Compartment Cell Study–
Authors: Yoshii Kazuki , Taguchi Noboru , Miyazaki Takeshi , Shikano Masahiro , Sakaebe Hikari 
Published: May 2020

Iron trifluoride (FeF3) has been attracted as one of the promising candidates for the positive electrode material of lithium secondary batteries due to their high theoretical capacity (712 mA g–1) and high energy density (1949 Wh kg–1). However, its poor cyclability and a large hysteresis of the voltage during charge and discharge still remain the problem to solve for the commercialization. The cycling performance of FeF3-based lithium secondary battery has been improved by various strategies, such as the addition of anion receptor, coating by other metals and tuning of electrolyte composition so far [1-3], but the suppression of degradation and the elucidation of its mechanism have not accomplished completely. In the present study, we investigated the charge and discharge behavior of the FeF3 positive electrode using a designed two-compartment type cell which has lithium ion-conducting ceramics as a separator to prevent the cross-talk of the electrolyte between the positive and negative electrode.
A charge/discharge test was performed using a coin cell and two-compartment type cell using 1.0 mol dm–3 LiPF6 in 1:1 ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) as the electrolyte. Disassembling analysis of both cells including SEM observation and X-ray fluorescence analysis revealed that the elution of Fe is more responsible for the degradation of the FeF3 electrode than a thick film formation on the electrode due to the cross-talk in the coin cell. Furthermore, the cyclability was improved using the electrolyte with LiDFOB as an additive for only the positive electrode side of the two-compartment type cell, whereas the improvement of the cyclability was not found when the additive was applied to a coin cell. After the cycling tests, various analyses, such as electrochemical impedance, X-ray photoelectron spectroscopy, and transmission electron microscopy, were also conducted for the electrode with and without additives in the electrolyte to examine the degradation mechanism of FeF3 positive electrode. The obtained results were considered useful for the improvement of the cycling performance of FeF3-based lithium ion batteries.
References
[1] K. Kumagae, K.-I. Okazaki, K. Matsui, H. Horino, T. Hirai, J.-I. Yamaki and Z. Ogumi, J. Electrochem. Soc., 163, A1633 (2016).
[2] Y. Li, X. Zhou, Y. Bai, G. Chen, Z. Wang, H. Li, F. Wu and C. Wu, ACS Appl. Mater. Interfaces, 9, 19852 (2017).
[3] H. Senoh, K. Matsui, M. Shikano, T. Okumura, H. Kiuchi, K. Shimoda, K. Yamanaka, T. Ohta, T. Fukunaga, H. Sakaebe and E. Matsubara, ACS Appl. Mater. Interfaces, 11, 30959 (2019).
Acknowledgement
This work was supported by the New Energy and Industrial Technology Development Organization (NEDO) under the “Research and Development Initiative for Scientific Innovation of New Generation Batteries 2 (RISING2)”
Ultra-Microporous Carbon Aerogel Encapsulating Sulfur As Cathode for Lithium-Sulfur Batteries
Authors: Nojabaee Maryam , Schwan Marina , Sievert Brigitta , Schettler Jessica , Wagner Norbert , Milow Barbara , Friedrich Andreas K 
Published: May 2020

The operating range and cost effectivity of electric vehicles are significantly compromised by the low energy density of state-of-the-art lithium-ion batteries. For the realization of electro-mobility, chemistries beyond Li-ion such as lithium-sulfur batteries offering high gravimetric energy density are requisite. However, the commercialization of Li-S batteries faces challenges such as severe capacity fade induced by the so-called polysulfide shuttle effect. Encapsulating and trapping the active material in the cathode matrix are among many approaches inhibiting polysulfide dissolution and shuttle effect [1-3].
Herein, we synthesized and investigated highly porous carbon aerogels (CA) as conductive matrix embedding sulfur for cathode in Li-S batteries [4]. Resulting from organic resorcinol-formaldehyde aerogels, the synthesised carbon aerogels exhibit highly porous structure with porosity up to 97%, high surface area of 500-2000 m²·g-1 and large micropore volume of 0.1-0.6 cm³·g-1. The gas-phase sulfur infiltration of the carbon aerogels and the resulting confinement of the short-chain sulfur in the micropores are demonstrated using complementary characterization techniques including TGA, XRD, and XPS. It is shown that S-infiltrated microporous carbon aerogel cathodes are able to suppress the polysulfide shuttle effect, maintaining 80% (1100 mAh/g(S)) of initial discharge capacity after 100 cycles at 0.3C in carbonate-based electrolyte. The cyclability and compatibility of the ether and carbonate-based electrolyte with such composite cathode are explicitly discussed. Additionally, the influence of chemical and physical properties of different synthesized carbon aerogels including pore density, size and morphology on the electrochemical behavior of the cell is investigated in detail.
1. S. Evers, & L. F. Nazar, New approaches for high energy density lithium–sulfur battery cathodes. Acc. Chem. Res. 46, 1135–1143 (2012).
2. Y. Yang, G. Zheng, Y. Cui, Nanostructured sulfur cathodes. Chem. Soc. Rev. 42, 3018–3032 (2013).
3. R. Fang, K. Chen. L. Yin, Z. Sun, F. Li, HM Cheng, The regulating role of carbon nanotubes and graphene in lithium-ion and Lithium-sulfur batteries, Advanced Materials, 31(9) 1800863 (2019)
4. Schwan und L. Ratke, "Flexible Carbon Aerogels" J. Carbon Res. 2, 22 (2016).
(Invited) Current Status and Bottlenecks of the Intercalation of Mg into Spinel Oxides
Authors: Cabana Jordi 
Published: May 2020

Electrochemical energy storage was an important enabler of the wireless revolution and it is touted as a key component of a society that shifts away from its dependence on fossil fuels. Li-ion batteries are the primary technology when high energy devices are required. However, despite their improved functionality over older systems (e.g. lead-acid car batteries), they do not quite yet meet the emerging energy demands in transportation and grid markets. This roadblock sparked interest in the development of batteries that utilize Mg2+ as ionic carrier. Theoretical predictions indicate that couples exist between a Mg metal negative electrode and oxide positive electrodes that could surpass the current practical limits of current devices. However, severe practical challenges have limited the study of the electrochemical properties of oxides to the simple elucidation of the viability and reversibility of the fundamental reactions of intercalation of Mg2+. Among the candidate oxides, the general family of spinel-type M2O4 (M=transition metal) are considered as leading contenders [1, 2]. In this talk, we will present the most up-to-date insight into the ability of spinel oxides to diffuse Mg2+. These observations will be paired with the outcomes of electrochemical reactions in non-aqueous electrolytes, since the use of Mg metal requires rigorously anhydrous environments. We will discuss the evidence supporting intercalation of Mg2+, and describe changes that correlate with both the identity of M and the existence of defects in the spinel structure [2, 3]. Critical to the endeavor is the ability to synthesize particles at small dimensions, as is the characterization of chemical and physical phenomena using a combination of tools providing information at different scales. The discussion will naturally lead us to reveal foundational bottlenecks that must be overcome to make Mg electrochemistry viable for energy storage.
1. Liu et al., Energy Environ. Sci.
2015, 8, 964.
2. Kim et al., Adv. Mater.
2015, 27, 3377.
3. Hu et al., Nanoscale
2019, 11, 639.
Electrolytes for Magnesium Batteries: Which Way to Go?
Authors: Jankowski Piotr , Garcia Lastra Juan Maria , Vegge Tejs 
Published: May 2020

Magnesium battery technology is one of the promising post-lithium technology, that has potential to reduce our lithium dependence, and at the same time outperform current Li-ion technology. Magnesium is more abundant, hence cheaper, and comes with promises of higher energy density and lower tendency to dendrite formation – possibility of metallic anode application. Higher capacity of such battery comes from double charge of magnesium ion, that also causes battery chemistry more difficult. Especially electrode/electrolyte interface becomes tricky, and simple transfer of electrolyte concept from lithium technology is not possible. Reversible plating/stripping of magnesium has been demonstrated many times, however in most of the cases from highly reactive and/or aggressive electrolytes. That put some obstacles on the way for future commercialization and a key challenge on the road to a rechargeable magnesium batteries is the development of non-corrosive magnesium electrolytes.
For some time, role of chloride in electrode process was considered to be essential for reduction of magnesium ions. However new studies show possible operation of magnesium battery with Cl-free electrolyte. Conditions for that are not completely clear, and here we are going to put some light on the processes occurring at electrode/electrolyte interfaces. DFT calculations are used to understand desolvation of magnesium ion, which is a key step prior to reduction at the electrode. Comparison of both systems, with standard and Cl-free electrolytes, shows the possibility to tune electrode process by changes in electrolyte composition, indicating the way towards the less reactive, and less corrosive systems.

Presented results were obtained within E-MAGIC project, which received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 824066.
Quest for Nanocrystal Spinel Oxides As Prospective Cathodes for Next-Generation Magnesium Batteries
Authors: Hu Linhua , Cabana Jordi 
Published: May 2020

Rechargeable batteries based on the intercalation of multivalent cations are a promising energy storage technology to overcome the limitations of safety, cost, and energy density of state-of-the-art Li-ion batteries. However, functionality of cathodes in Mg batteries has only been realized with a few of S-containing compounds, which possess limited capacity and operate at low potential, hindering competitive energy densities. Spinel oxides have been predicted to improve both voltage and capacity. However, the strong electronic interaction between these cations and the corresponding frameworks impose the challenge of Mg2+ low mobility and sluggish kinetics.
Herein, a series of spinel oxides with designed sizes and defects have been evaluated as possible cathodes, studying their fundamental ability to intercalate Mg2+ by using different temperatures. Mg2+ deintercalation at high voltage was achieved at 110oC, and, under certain conditions, even at room temperature. In addition, the capabilities of Mg2+ reversible intercalation are correlated to particle size. Our results demonstrate that the design of nanosized spinel oxides could enable an efficient pathway to improve Mg2+ reaction kinetics, thus advancing the ability to develop new multivalent cathode protypes with high energy density.
References:
1. Liu, M., Rong Z., Malik, R., Canepa P., Jain A., Ceder G., Persson K. Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations. Energy Environ. Sci. 2015, 8, 964.
2. Kim C., Phillips P. J., Key B., Yi T., Nordlund D., Yu Y.-S., Bayliss R. D., Han S., He M., Zhang Z., Burrell A. K., Klie R. F., Cabana J. Direct Observation of Reversible Magnesium Ion Intercalation into a Spinel Oxide Host. Adv. Mater. 2015, 27, 3377.
3. Hu, L., Johnson I.D., Kim S., Nolis G.M., Freeland J.W., Yoo H.D., Fister T., McCafferty L., Ashton T., Darr J., Cabana J. Tailoring the electrochemical activity of magnesium chromium oxide towards Mg batteries through control of size and crystal structure. Nanoscale 2019, 11, 639.
Transient Behavior in Phase-Transforming Electrodes Revealed By Operando X-Ray Diffraction
Authors: Deng Haitao , Jin Norman , Zhao Hongbo , Lim Kipil , Lomeli Eder , Takacs Christopher J , Bazant Martin Z. , Chueh William C. 
Published: May 2020

Solid state phase transformation triggered by lithium insertion is ubiquitous in many commercially available battery electrodes such as LiXFePO4 (LFP), LiXCoO2 and graphite. Understanding the kinetics of phase transformation, in particular the nucleation and growth of a second phase due to the Li compositional changes is key to achieving high cycling rates in these phase separating materials. LFP is a model phase transforming material with a large miscibility gap that thermodynamically favors phase separation (segregation into Li-rich and Li-poor phases) in bulk crystals of sizes larger than 50 nm.
It’s commonly accepted that phase transformation at constant current happens via two major pathways: (1) particle-by-particle transformation with a moving interface and (2) concurrent transformation, mediated by a kinetically stabilized solid solution[1-4]. However, realistic battery operation involves erratic charging and discharging behavior such as brief pulses, rests, etc, wherein our current understanding is still lacking. Primarily the relationship between particle dynamics (i.e. the solid solution fraction, active particle population) in an electrode and applied overpotential remains unclear. We herein combine operando X-ray diffraction and numerical phase field simulation to track and understand the transient response of the battery particles during non-constant current conditions. This work highlights the importance of particle dynamics for phase separating electrodes in operation and inspires general battery operating principles that prolong cycle life.

References

[1] Li, Yiyang, et al. Nature materials 13.12 (2014): 1149.
[2] Liu, Hao, et al. Science. 344.6191 (2014): 1252817.
[3] Li, Yiyang, et al. Nature materials 17.10 (2018): 915.
[4] Bazant, Martin Z, et al. Acc. Chem. Res. 46.5 (2013): 1144-1160.