bluuebunny/crossref_metadata_2025_split huggingface dataset:
Elemental Sulfur Mediated Facile Synthesis of a Colvalent Triazine Framework for High Performance Lithium-Sulfur Batteries
Authors: Hwang Tae Hoon , Talapaneni Siddulu Naidu , Coskun Ali , Choi Jang Wook 
Published: February 2020

Sulfur is one of the most abundant elements and more than 70 million tons of elemental sulfur is annually produced as a by-product of the hydrodesulfurization process in the petroleum refining industry. This mostly involuntary production of sulfur, however, creates a significant global supply surplus. Therefore, the development of highly functional sulfur-rich polymers that are synthesized via direct utilization of elemental sulfur can be a useful direction in recycling the abundant sulfur to high value outcomes. Rechargeable lithium–sulfur (Li-S) batteries have received significant attention in recent years as one of such opportunities owing to their high theoretical gravimetric capacity and energy density of 1,675 mAh g-1 and 2,567 Wh kg-1, respectively. However, despite almost 30 years of development, Li-S batteries are still at the research stage, because of insufficient cycle life mainly due to the fatal redox shuttling process originating from the dissolution of the intermediate lithium polysulfide species in most of operating organic electrolytes during charge/discharge process.
Herein, we report, for the first time, sulfur-medidated synthesis of CTF-1 (S-CTF-1) using 1,4-dicyanobenzene and elemental sulfur without any catalysts or solvents. The formation of CTF engages in-situ vulcanization with elemental sulfur, enabling both covalent attachment of sulfur and its homogeneous distribution within the pores. S-CTF-1 was found to have a high sulfur content of 62 wt% along with a well-shaped bipyramidal morphology that has been achieved without using any external template. We have also examined electrochemical performance of S-CTF-1 as a sulfur-cathode material in Li-S batteries. S-CTF-1 exhibited robust cycling performance for 300 cycles with 85.8% capacity retention along with the highest initial Coulombic efficiency (ICE) reported to date: 94.4% at 0.05C (25 mA g-1). Our results demonstrate the promising aspect of microporous polymers as active supports for sulfur, thus it is expected to motivate further research in this area. In a broader perspective, direct utilization of elemental sulfur in the synthesis of covalent triazine frameworks can open up new high-value applications, such as advanced electrode materials for energy storage and conversion.
Magnesium/Sulfur Rechargeable Batteries Using Liquid Mg Polysulfides
Authors: Vinayan Bhaghavathi Parambath , Cambaz Musa Ali , Zhao-Karger Zhirong , Fichtner Maximilian 
Published: February 2020

Rechargeable magnesium (Mg) batteries are a sustainable option for electrochemical energy storage of renewable energy due to the inherent merits associated with Mg such as natural abundance, operational safety and high theoretical volumetric capacity (3,832 mAh cm-3), with a reduction potential of − 2.356 V versus normal hydrogen electrode (NHE).1 Among different types of cathode materials, the combination of Mg with a sulfur cathode and a non-nucleophilic electrolyte is very promising due to its large theoretical energy density of about 3200 Wh l−1, based on a two-electron conversion reaction expressed as, Mg2+ + S + 2e − ↔ MgS, which is beyond that of a Li/S battery (2800 Wh l-1). In addition, these battery systems are reversible and using low cost materials. Compared to the progress made on Li/S batteries, the Mg/S battery is still in a very early stage of research and development due to number of reasons such as low kinetics of Mg, lack of suitable electrolytes, polysulfide dissolution, insulating nature of sulfur, capacity fading etc.
Herein, we demonstrate a reversible Mg dissolved polysulfide cell using reduced graphene oxide (rGO) as the cathode host matrix and a non-nucleophilic Mg electrolyte in tetraglyme solution as the electrolyte. The electrolyte was prepared by mixing a non-nucleophilic base of magnesium-bis(hexamethyldisilazide) [(HMDS)2Mg] with the Lewis acid, AlCl3 (1:2 molar ratio) and dissolving the reaction product in a tetraglyme (C10H22O5) ethereal solvent . The liquid Mg polysulfides cell delivers better reversible capacity (~750 mAh g-1, Figure. 1) and cyclability as compared to previous Mg/S cell reports. The high surface area, porous structure and presence of oxygen functional groups over rGO give simultaneous physical and chemical adsorption of Mg polysulfides with the host matrix. Further, the working mechanism of liquid Mg polysulfides within Mg/S cell is investigated by Raman spectroscopy.

References

[1] H. S. Kim, T. S. Arthur, G. D. Allred, J. Zajicek, J. G. Newman, A. E. Rodnyansky, A. G. Oliver, W. C. Boggess and J. Muldoon, Nat. Commun., 2011, 2, 427.
[2] B. P. Vinayan, Z. Zhao-Karger, T. Diemant, V. S. K. Chakravadhanula, N. I. Schwarzburger, M. A. Cambaz, R. J. Behm, C. Kubel and M. Fichtner, Nanoscale, 2016, DOI: 10.1039/C5NR04383B.

Figure 1
Structural View of Li Ion and Electron Correlation in Li2FeSiO4 Cathode
Authors: Lu Xia , Chiu Hsien-Chieh , Arthur Zachary , Wei Huijing , Zhou Jigang , Wang Jian , Chen Ning , Jiang De-Tong , Zaghib Karim , Demopoulos George P. 
Published: February 2020

Orthosilicates, Li2

M
SiO4, where
M

= Fe, Mn, Co, Ni, are characterized by a theoretical specific capacity that is twice that of LiFePO4, namely 340 vs. 170 mAh/g. In this presentation, we have probed the structural evolution and charge compensation of Li2FeSiO4 cathode using both in-situ/postmortem synchrotron XRD/XANES and first-principle calculations1-3. The results demonstrate that the formation of Li-Fe antisite defects play a key role in destabilizing the Li2FeSiO4 structure and “catalyzing” the monoclinic-to-orthorhombic transition. Then the charge compensation for the first Li extraction does not come solely from the ferrous to ferric conversion due to the strong electron correlation of Fe 3d orbitals, but interestingly from prominent participation of lattice oxygen as well that appears to destabilize the cycled structure. Using scanning transmission X-ray microscopy, it is revealed that the electrochemical lithiation/delithiation of Li2FeSiO4 electrode does not proceed uniformly but it exhibits an unusual solid solution pattern4 with the stored Li content varying locally possibly arising from a combination of inherent LFS material and electrode properties like poor conductivities, variable particle size/distribution and extent of electrolyte penetration. All these findings should have a thought-provoking influence on the study of the material itself and the broader Li-ion battery research community as well.
References
1. Lu, X.; Wei, H. J.; Chiu, H. C.; Gauvin, R.; Hovington, P.; Guerfi, A.; Zaghib, K.; Demopoulos, G. P. Rate-dependent phase transitions in Li2FeSiO4 cathode nanocrystals. Sci Rep-Uk 2015, 5, 8599.
2. Arthur, Z.; Chiu, H.-C.; Lu, X.; Chen, N.; Emond, V.; Zaghib, K.; Jiang, D.-T.; Demopoulos, G. P. Spontaneous reaction between uncharged lithium iron silicate cathode and LiPF6-based electrolyte Chem Commun 2015, accpeted, DOI: 10.1039/C5CC07197F.
3. Lu, X.; Chiu, H.-C.; Bevan, H. K.; Jiang, D.-T.; Zaghib, K.; Demopoulos, P. G. Density functional theory insight into the structure stability and Li diffusion properties of monoclinic and orthorhombic Li2FeSiO4 cathodes. J Power Sources 2015, In revision.
4. Lu, X.; Chiu, H.-C.; Arthur, Z.; Zhou, J. G.; Wang, J.; Chen, N.; Jiang, D.-T.; Zaghib, K.; Demopoulos, G. P. Quasi-equilibrium Li storage in metastable Li2FeSiO4 cathode. 2015, Under review.
Li4SnS4: Simulations of Its Structure and Electrolyte Properties
Authors: Holzwarth Natalie A. W. 
Published: February 2020

Recent literature [1,2,3,4] reports the use of Li4SnS4 and its alloys as a relatively stable solid electrolyte for use in all-solid-state Li batteries. This poster presents results of first-principles simulations of the ideal crystalline structures and of defects associated with Li ion migration in this material. The simulations find that the lowest energy
structure of the idealized crystal is consistent with the structure determined by MacNeil et at. [2] from samples synthesized at high temperature (750 deg C). The simulations also find a slightly higher energy structure which is consistent with the structure determined by Kaib et al. [1] from samples prepared at lower temperature (320 deg C), processed from solution. Simulations of the Li ion migration properties of the two structures are compared.
Acknowledgements
This work was supported by NSF grant DMR-1507942 and by the Wake Forest University DEAC Computer Cluster. Joseph MacNeil and Jennifer Aitken contributed additional information about the experimental details.
[1]Thomas Kaib, Sima Haddadpour, Mauel Kapitein, Philipp Bron, Cornelia Schroeder, Hellmut Eckert, Bernard Roling, and Stefanie Dehenen, Chemistry of Materials, 24, 2211-2219 (2012)
[2]Joseph H. MacNeil, Danielle M. Massi, Jian-Han Zhang, Kimberly A. Rosmus, Carl D. Brunetta, Taylor A. Gentile, and Jennifer A. Aitken, Journal of Alloys and Compounds, 586, 736-744 (2014)
[3] Gayatri Sahu, Zhan Lin, Juchuan Li, Zencai Liu, Nancy Dudney, and Chengdu Liang, Energy & Environmental Science, 7, 1053-1058 (2014)
[4] Kern Ho Park, Dae Yang Oh, Young Eun Choi, Young Jin Nam, Lili Han, Ju-Young Kim, Huolin Xin, Feng Lin, Seung M. Oh, and Yoon Seok Jung, Advanced Materials, DOI: 10.1002/adma.201505008
Free-Standing Nitrogen-Rich Carbonization Polypyrrole Films As Advanced Anode for Lithium-Ion Batteries
Authors: Yuan Tao , Zhang Weimin , He Yu-Shi , Zheng Shiyou , Ma Zi-Feng 
Published: February 2020

Recently, for the pursue of high energy density of Li-ion battery system and more lightweight and flexible battery for potential applications in flexible electronic devices such as wearable devices, artificial electronic skins, and distributed sensors, an extensive research effort is underway to produce soft free-standing electrode-active materials without binder and conductive agent for such bendable batteries.[1-3]
We propose here an N-rich pure carbon film synthesized by calcining vapour phase polymerized polypyrrole (PPy) film as an anode for Li-ion battery.[4] The PPy precursor film was synthesized via a simple vapor phase polymerization (VPP) bottom-up assembly method using Fe(III) tosylate oxidant (Figure 1). The obtained PPy film shows smooth surface and continuously cross-linked structure. After carbonized at high temperature at inert atmosphere, a continuously cross-linked carbon film doped with nitrogen can be formed. The carbonization process of PPy film precursor was result in large numbers of uniform mesopores in N-C film, which is expected to provide very regular pore channels for Li+ charge transfer and storage. The as-derived free-standing nitrogen-containing carbon film anode exhibits excellent electrochemical performance, especially, at high charge/discharge rate for lithium-ion batteries. The reversible capacities are 908.4, 825.7, 664.0, 531.6, 415.5 and 325.9 mAh g-1at 1C, 2C, 5C, 10C, 20C and 40C, respectively. The N-C film anode also shows excellent cyclability with high capacity. After 800 cycles, the reversible capacity retains 91.6% of the initial stage. The coulomb efficiency is close to 100%. Such free-standing flexible N-C film anode can be straightforwardly used to fabricate the lithium-ion batteries which are required to deliver high energy and power.
Acknowledgements:
We are grateful for financial support for this work from the National Basic Research Program of China (2014CB239700), the Natural Science Foundation of China (21336003, 21403139, 51472161, 51472160), the Shanghai Pujiang Program (No. 14PJ1407100) and the Science and Technology Commission of Shanghai Municipality (14DZ2250800, 15JC1490800, 12JC1406900, 14520721700). We acknowledge the support of the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning (TP2014048) and the Hujiang Foundation of China (B14006).
References:
[1] S. Zheng, Y. Chen, Y. Xu, F. Yi, Y. Zhu, Y. Liu, J. Yang, C. Wang, ACS nano, 10995-11003, 7 (2013).
[2] Y. Xu, Q. Liu, Y. Zhu, Y. Liu, A. Langrock, M.R. Zachariah, C. Wang, Nano lett., 470-474, 13 (2013).
[3] T. Yuan, B. Zhao, R. Cai, Y. Zhou, Z. Shao,
J. Mater. Chem.,
15041-15048, 21 (2011).
[4] T. Yuan, Y-S. He, W. Zhang, Z-F. Ma, Chem. Commun., 112-115, 52 (2016).

Figure 1
Role of the Transition Metal in Intermetallic Anodes
Authors: Vaughey John T. 
Published: February 2020

Intermetallic anodes are a small but important subclass of lithium-ion battery anode materials. In general materials in this class represent a compromise in terms of capacity and voltage compared to commercial materials but also tend to be crystallographically denser and have more stable cycling profiles. Common examples include Cu2Sb, Cu6Sn5, and MnP [1-5]. They operate by inserting and storing lithium at low voltages using a variety of mechanisms that combine aspects of the main storage mechanisms. Intercalation anodes (e.g. graphite) insert lithium into existing crystallographic vacancies, conversion anodes store lithium in binary compounds formed by a disproportionation reaction, and Zintl phases react with lithium to form distinct crystallographic phases that undergo large bonding and volume changes as a function of lithium content [6]. In this presentation, a variety of intermetallic anodes will be assessed to better understand the role of the transition metal in allowing these materials to utilize multiple mechanisms to store lithium. Knowledge gained from this analysis will be used to predict and better understand new high density anode materials.
[1] A. N. Jansen, J. A. Clevenger, A. M. Baebler, J. T. Vaughey J. Alloys Compounds
509 4457–4461 (2011)
[2] Keith D. Kepler, John T. Vaughey, M. M. Thackeray Electrochem. Sol State Lett., 2 307-309 (1999).
[3] Seung-Wan Song, R. P. Reade, E. J. Cairns, J. T. Vaughey, M. M. Thackeray, K. A. Striebel J. Electrochemical Soc., 151 (2004) A1012-A1019.
[4] L.M. L. Fransson, J. Vaughey, R. Benedek, K. Edstrom, J. O. Thomas, M. Thackeray Electrochem. Comm.
3 (2001) 317-323.
[5] D. C. S. Souza, V. Pralong, A. J. Jacobson, L. F. Nazar Science
296 (2002) 296, 2012.
[6] V. Aravindan , Y.-S. Lee, S. Madhavi Adv. Energy Mater. (2015) 1402225.

Figure 1
Improved Performance for Lithium Rich Layered Oxides Via High Throughput Technologies
Authors: Carroll Kyler J. , Li Bin , Strand Dee 
Published: February 2020

The design of high voltage and high capacity cathode materials for lithium ion batteries is important for the pressing demands of both electric vehicles and portable devices. Lithium excess layered oxides, where the lithium-to-transition metal ratio is greater than 1, have been widely explored due to the possibility of utilizing more than 1 lithium in the chemical formula unit to significantly increase the capacity. Despite much research, commercial application of the lithium excess material has been impeded due to low initial coulombic efficiency, poor cycle life, voltage fade, and poor rate performance. These deficiencies have mainly been attributed to the complicated structural evolution and the formation of a cathode solid electrolyte interface (SEI) layer at higher voltages (>4.5V). Therefore, the role of surface modification on improving the electrochemical properties has been investigated by Wildcat.
The use of chemical treatments and post-annealing steps to induce the formation of a surface spinel structure prior to electrochemical cycling can improve the first cycle coulombic efficiency and rate performance. However, further improvements in the first cycle coulombic efficiency and cycle life of these materials are still required. This work investigates several families of surface coatings and compositional dopants in lithium rich layered oxides. Modification of the surface coating and addition of dopants can greatly enhance the first cycle coulombic efficiency while also maintaining or improving cycle stability, voltage fade, and rate performance of the lithium excess material. Wildcat evaluation of the performance of hundreds of surface coatings and dopants shows that certain families tend to improve all metrics. In addition we have demonstrated that certain families, such as metal phosphate and metal fluoride coatings, reduce gas generation during the first cycle as well as subsequent cycles relative to the pristine lithium excess material.
Design and Processing of Advanced Lithium-Ion Electrode Materials
Authors: Yonemoto Bryan T , Shin Youngho , Croy Jason R. , Thackeray Michael M. 
Published: February 2020

Significant interest in lithium- and manganese-rich (LMR) cathodes exists within the lithium-ion battery community. LMR electrodes, which incorporate a Li2MnO3 motif into the structure [1], exhibit high capacities and have relatively low raw materials costs [2]. Despite these attributes, significant challenges to commercialization remain, including industrial considerations related to materials processing. Synthesis of commercialized materials and electrodes such as those based on LiCoO2 (LCO) and LiNi­0.8Co0.15Al0.05O2 (NCA) has been highly optimized. However, less work has been done on the optimization and processing of promising new LMR compositions. Specifically, structurally-integrated “layered-layered-spinel” cathodes have been shown to provide improved rate capability, first-cycle efficiency, and possibly structural stability with cycling than their “layered-layered” counterparts [3]. However, these new chemistries have to date received little attention in the way of optimizing electrochemical performance through improved particle synthesis. This poster will detail important considerations for LMR particle synthesis through reactive crystallization, and highlight ongoing work at Argonne National Laboratory on the design and synthesis of advanced lithium-metal-oxide electrode materials.

References

M. M. Thackeray, C. S. Johnson, J. T. Vaughey, N. Li and S. A. Hackney, J. Mater. Chem. 15, 2257 (2005).

K. G. Gallagher, S. Goebel, T. Greszler, M. Mathias, W. Oelerich, D. Eroglu, V. Srinivasan, Energy & Environ. Sci. 7, 1555 (2014).

B.R. Long, J. R. Croy, J.S. Park, J. Wen, D.J. Miller and M.M. Thackeray, J. Electrochem. Soc. 161, A2167 (2014).

Acknowledgments

Funding for this work from the Office of Vehicle Technologies of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged.
The submitted abstract has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy 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.
Experimental and Theoretical Study of Fe-V Redox Flow Battery
Authors: Hammad Ahmad D , Souentie Stamatios , Amr Issam T , Alsuhaibani Abdulrahman S 
Published: February 2020

Energy storage is currently one of the major challenges for the deployment of renewable resources. A low cost, flexible, large-scale technology is required to store and buffer the fluctuated electricity production rate. The Redox Flow Battery (RFB) is a very promising candidate with long life-span, high efficiency, and suitability for large scale energy storage, enhancing the reliability of the power grid, and promoting energy independence of remote areas. One additional substantial advantage of RFBs is that power and energy can be independently adjusted. The current cost of conventional flow battery systems is relatively high. This is due to the use of expensive vanadium-base electrolytes, along with Nafion-based membranes.
In this study, the V5+/V4+ redox couple has been replaced with the Fe3+/Fe2+, which results in significant cost reduction. The illustrated Fe-V battery employs an FeCl2 in HCl(aq) catholyte in one tank, and VCl3 in HCl(aq) anolyte in the other tank. A graphite electrochemical cell was equipped with a Nafion® 117 membrane, on which two carbon felt electrodes were attached. A galvanostat/potentiostat was used to apply constant currents and potentials. In this direction, an experimental and theoretical analysis of the iron-vanadium flow battery was carried out, investigating the effect of temperature, charge/discharge rate, and state of charge on the performance/efficiency of the energy storage system. To characterize the battery, voltage efficiency measurements and polarization curves were carried out at each point. In this way, the suitable operation SOC range for employed loads that the battery serves, can be defined for best voltage efficiency and power output.
The charge/discharge characteristics of the battery reveal an optimum operation temperature at ~47oC and an optimum charging current of ~50mA/cm2 for the state of charge range between 20% and 80%. Also, a small increase in the open circuit voltage with charging current was observed, indicating a slightly higher charging depth. The voltage efficiency as obtained by the finite-time galvanostatic charge and discharge cycles, strongly depends on the current J that is used. Efficiency measurements were performed for various SOC values using J from 300 to 800mA at 42oC. Moreover, voltage and coulombic efficiencies achieve up to 85%.
A mathematical model was built, based on the current exchange density obtained by the polarization curves for various operation conditions of the battery. The model concludes a negative asymmetry form to the energy barrier, to rate the determining half-reaction.
(Invited) Plasmon-Induced Charge Separation and Electric Field Localization
Authors: Tatsuma Tetsu , Saito Koichiro , Ishida Takuya , Nishi Hiroyasu 
Published: February 2020

Plasmon-induced charge separation (PICS) occurs at the interface between plasmonic nanostructures of Au, Ag, or Cu and a semiconductor (e.g., TiO2).1-3 Carrier transfer from the nanostructure to the semiconductor due to external photoelectric effects (including hot carrier injection) or interfacial electron transition is responsible for PICS.4 We reported PICS for the first time more than 10 years ago1,2 and studied its mechanisms4,5 and applications.1,3,6,7 In particular, we have reported effects of localized electric field on PICS. In the case of PICS-based oxidation of Ag nanoparticles, anodic reaction (i.e., oxidation of Ag to Ag+) occurs preferentially at the sites where optical near field is localized.8-10 This may be explained in terms of ejection of energetic holes from the nanoparticles as Ag+ ions.10

1. Y. Tian and T. Tatsuma, J. Am. Chem. Soc., 127, 7632 (2005).
2. Y. Tian and T. Tatsuma, Chem. Commun., 2004, 1810.
3. T. Tatsuma, Bull. Chem. Soc. Jpn., 86, 1 (2013) [account].
4. E. Kazuma and T. Tatsuma, Adv. Mater. Interfaces, 1, 1400066 (2014).
5. H. Nishi and T. Tatsuma, Angew. Chem. Int. Ed., 55, 10771 (2016).
6. Y. Ohko, T. Tatsuma, T. Fujii, K. Naoi, C. Niwa, Y. Kubota, and A. Fujishima, Nat. Mater.,
2, 29 (2003).
7. Y. Takahashi and T. Tatsuma, Appl. Phys. Lett., 99, 182110 (2011).
8. E. Kazuma, N. Sakai, and T. Tatsuma, Chem. Commun., 47, 5777 (2011).
9. I. Tanabe and T. Tatsuma, Nano Lett., 12, 5418 (2012).
10. K. Saito, I. Tanabe, and T. Tatsuma, J. Phys. Chem. Lett., 7, 4363 (2016).