bluuebunny/crossref_metadata_2025_split huggingface dataset:
Programming the Knowledge: A Trial QSAR Study Towards the Stability of Dialkoxy Benzene Based Catholyte Molecules for Nonaqueous Redox Flow Batteries
Authors: Zhang Lu , Zhang Jingjing , Silcox Benjamin , Shkrob Ilya A , Assary Rajeev , Cheng Lei , Thompson Levi 
Published: February 2020

Programming the knowledge: A trial QSAR study towards the stability of dialkoxy benzene based catholyte molecules for nonaqueous redox flow batteries
Lu Zhang1, Jingjing Zhang1, Benjamin Silcox3, Illya A. Shkrob1, Rajeev S. Assary2, Lei Cheng2, Levi Thompson4

1Chemical Sciences and Engineering Division, 2Material Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, United States

3Chemical Engineering, University of Michigan, 500 S State St, Ann Arbor, MI 48109, United States

4Department of Chemical and Biomolecular Engineering, University of Delaware,Newark, DE 19716, Unite States
The stability of redox active molecules is a paramount property that dramatically affects the cycling performance in redox flow batteries. Computationally, it requires huge amount of resource to exhaustively iterate all the possible degradation pathways in order to estimate the stability of active species, such as radical cations.1 QSAR, or quantitative structure–activity relationship, provides an interesting approach to correlate chemical structures and properties based on the idea of property changes are all coming from structure modifications. While this approach simplified the insightful analysis of the detailed mechanism, it becomes particular useful to simulate or even predict complex properties, such as the stability of redox molecules. In this talk, we developed a series of dialkoxy benzene based catholyte molecules that are of potential use to nonaqueous redox flow batteries and systematically changed their substitutions on the alkoxy moieties. Then their electrochemical/chemical properties, including redox potential, charged state stability (reflected by EPR life time), and even cycling numbers, have been characterized and analyzed. Importantly, a number of descriptors have been identified based on our long accumulated knowledge regarding stability of the charged radical cations. Finally, a linear regression model was established using those descriptors to simulate the EPR life time, and even cycling numbers and the resulted fittings delivered quite satisfactory correlation between the selected descriptors and properties. While this is only a trial study based on a small set of molecules, the QSAR approach proves to be useful in understanding complex properties for redox active molecules, which could stimulate further understanding and development of such promising materials.

Assary, R. S.; Zhang, L.; Huang, J.; Curtiss, L. A., Molecular Level Understanding of the Factors Affecting the Stability of Dimethoxy Benzene Catholyte Candidates from First-Principles Investigations. The Journal of Physical Chemistry C
2016,
120 (27), 14531-14538.
Zinc Anode Design for Rechargeable Aqueous High-Energy Zn Batteries
Authors: Zhang Yamin , Wu Yutong , Yan Yu , Zhou Zhubo , Liu Nian 
Published: February 2020

As an energy storage system, Li-ion batteries are not safe because they use flammable organic electrolytes. A safer alternative is rechargeable Zn-based batteries with aqueous electrolytes. Among them, Zn-air batteries have high theoretical volumetric energy density (4400 Wh/L), which can even compete with lithium-sulfur batteries. Alkaline electrolyte is preferable for Zn-air batteries. However, the performance of Zn anodes in alkaline electrolyte is limited by passivation, dissolution and hydrogen evolution. Through SEM investigation, critical passivation size was found to be ~ 2 µm. Sub-micron-sized Zn anodes won’t have passivation problem. As a result, we focus our research on nanoscale. However, Zn dissolution of nanosized anodes will be accelerated because of large electrode-electrolyte surface area.
Thus, anode modification and protection are needed to alleviate the dissolution. We designed a (1) Zn mesh@GO anode (Fig. 1a): graphene oxide (GO) layers on the Zn mesh surface deliver electrons across insulating ZnO and can slow down the Zn dissolution; (2) lasagna-inspired ZnO@GO anode (Fig. 1b): ZnO nanoparticles encapsulated by GO can solve simultaneously the passivation and dissolution problems; (3) core-shell ZnO@TiN nanorod anode (Fig. 1c): thin and conformal TiN coating mitigates Zn dissolution, mechanically maintains the nanostructure, and delivers electron to nanorods. These coatings are ion selective, which allow permeation of OH- and water, and prevents loss of Zn active material through blocking bigger Zn(OH)4
2-.
Hydrogen evolution is a competitive side reaction on the zinc anodes, which causes low efficiency of Zn based batteries. Two approaches are investigated to suppress hydrogen evolution, including (1) modify the anode with a hydrogen suppressive material: core-shell ZnO@TiO2 nanorod anode was made with hydrogen suppressive TiO2 coating, which solves hydrogen evolution, passivation and dissolution problems at the same time; (2) design a hydrogen evolution suppressive nanostructured alloy anode: Zn-Ag alloy with increased standard reduction potential was used, which is more competitive compared with hydrogen evolution and more stable in aqueous electrolyte.
All of these anodes show superior performance compared with unmodified anodes. These anodes can be paired with air cathodes to make high energy Zn-air batteries. The nanoscale design principles here can potentially be applied to overcome intrinsic limitations of other battery materials.

Figure 1
Determining Interphase Identity and Directing Cation Transport Properties at Mg and Ca Electrodes
Authors: Zavadil Kevin R , Hahn Nathan T , Feng Xuefei , Liu Yi-Sheng , Guo Jinghua 
Published: February 2020

Regulating cation transmission at electrode interfaces is an essential function required for realizing storage based on multivalent working ions, including Mg and Ca. Cation transmission regulating interphases are believed to exist at both anode and cathodes surfaces for a host of electrolytes based on ethereal solvents, contributing to energetic barriers to cation accommodation at metal deposits and (de)insertion into cathodes. These interphases are derived from supporting electrolyte anion, solvent or impurity decomposition or more complex synergistic reactions. Weakly coordinating anions, of defined reductive/oxidative stability in highly purified form, provide an opportunity to explore the origin and consequences of reactivity and interphase formation. In this presentation, we describe several examples where origin of reactivity has been successfully probed through electrolyte constituent control and application of operando (e.g., electrochemical X-ray absorption) and ex situ (e.g., analytical transmission electron microscopy) methods. Results highlight critical phases and distributions responsible for cation transport and provide new insight into directing interphase formation to facilitate cation transport enhancing electrode performance.
This work was supported as part of the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and 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-NA-0003525.
Going Beyond Intercalation Capacity of Aqueous Metallic Zn-Anode Batteries
Authors: Yadav Gautam Ganapati 
Published: February 2020

Research interest on zinc (Zn)-anode aqueous-based batteries have renewed recently because of its low equilibrium potential in aqueous electrolyte, low cost, non-toxic and nonflammable characteristics compared to lithium-ion batteries. Zn has a high theoretical capacity of 820mAh/g based on two electron reactions, thus it has the capacity to deliver high energy density if it is paired with an equally high capacity cathode. Silver and nickel are high capacity cathodes; however, they are very expensive and require the addition of expensive additives like cobalt in nickel to increase the rate of the battery. MnO2 is the best cathode to be paired with Zn because it has a high two electron capacity of 617mAh/g and it is extremely safe and economical. Recently, we showed that attaining the two electron capacity of 617mAh/g for over 3000 cycles was possible with the used of bismuth and copper additives. Energy densities >160Wh/L were attainable when the cathodes were paired with Zn at 15% utilization.1-5 However, they are still susceptible to Zn poisoning which lead to the formation of inactive phase called haeterolite (ZnMn2O4). To improve the energy densities of Zn-anode batteries new inexpensive and safe cathodes with higher capacity than MnO2 and increasing Zn utilizations to >20-25% are a must.
In this presentation, we will report the synthesis of a new Mn-based cathode that delivers capacity ~800mAh/g, which is almost comparable to the Zn anode theoretical capacity. This new Mn-based cathode is able to deliver its capacity at high rates and maintain its capacity at high cycle life. We will present the reaction mechanism of this Mn-based cathode through real time microscopy videos and images, high resolution transmission microscopy and electroanalytical methods. We also report on the use of new Zn-based anodes that utilize >90% of its theoretical capacity and, at the time of this writing, still cycle with much deterioration in capacity due to shape change or passivation. The combination of the new high capacity Mn-based cathode and high utilization Zn-based anode results in a cell that delivers energy density >210Wh/L.
References:
1] Gallaway, J. W.; Hertzberg, B. J.; Zhong, Z.; Croft, M.; Turney, D. E.; Yadav, G. G.; Steingart, D. A; Erdonmez; C. K.; Banerjee, S. Journal of Power Sources, 2016, 321, 135-142
2] Huang, J.; Yadav, G. G.; Gallaway, J. W.; Wei, X.; Nyce, M.; Banerjee, S., Electrochemistry Communications, 2017, 81, 136-140
3] Yadav, G. G.; Gallaway, J. W.; Turney, D. E.; Nyce, M.; Huang, J.; Wei, X.; Banerjee, S., Nat. Commun., 2017, 8, 14424
4] Yadav, G. G.; Wei, X.; Huang, J.; Gallaway, J. W.; Turney, D. E.; Nyce, M.; Secor, J.; Banerjee, S., J. Mater. Chem. A, 2017, 5 (30), 15845-15854
5] Yadav, G. G.; Wei, X.; Gallaway, J. W.; Chaudhry, Z.; Shin, A.; Huang, J.; Yakobov, R.; Nyce, M.; Vanderklaauw, N.; Banerjee, S. Materials Today Energy, 2017, 6, 198-210.
(Invited) Pushing the Capacity of Layered Oxide Cathode to the Limit
Authors: Yang Lufeng , Li Xiang , Xiong Shan , Hu Yan-Yan , Chen Hailong 
Published: February 2020

Na-ion batteries are being extensively investigated as one of the possible alternatives to very popular Li-ion batteries. Compared with Li-ion batteries, Na-ion batteries have the advantage in cost, because of the much higher natural abundance and availability of Na than Li, which makes Na-ion batteries potentially a candidate for gird level energy storage. However, currently the energy density of Na-ion batteries is in general lower than those of Li-ion batteries, limited by multiple components in the cell, majorly by the cathode. Currently, most high capacity cathodes for Na-ion batteries are layered oxides with a general formula NaxMO2, where M is a transition metal or the combination of transition metals. Most of the layered oxide cathodes, however, can only stably cycle at <50% of their theoretical capacities, which greatly limits the energy density of the full cell.[1, 2] What is the limit of energy density of Na-ion batteries in current configuration? How to push the capacity of layered oxide cathodes to its theoretical limit? These are the questions to be addressed towards the goals of using Na-ion batteries to replace Li-ion batteries. In this work, we explored the fundamental reasons that limit the reversible capacity of layered oxide cathodes and demonstrated a new strategy to push their capacity to the limit, with using a group of rationally designed compounds as examples. A series of oxides, including Na0.66(Li0.2Mn0.2)O2 [3] and Na0.66Li0.18Fe0.12Mn0.7O2, etc. were designed to verify the proposed strategies and these compounds were successfully synthesized in desired P2 type layered structures. Many of these compounds demonstrated high cycling capacities ranging from 190 to 230 mAh/g, which are very close to the theoretical limit. In-depth structure characterizations with using in situ and ex situ synchrotron X-ray diffraction, neutron diffraction and solid state NMR were performed, in order to reveal the functioning mechanism of these compounds and provide more guidance to the materials design to further improve the capacity, voltage and cycling stability of the cathode materials.
[1] B.L. Ellis, L.F. Nazar, Sodium and sodium-ion energy storage batteries, Current Opinion in Solid State & Materials Science, 16 (2012) 168-177.
[2] S.P. Ong, V.L. Chevrier, G. Hautier, A. Jain, C. Moore, S. Kim, X.H. Ma, G. Ceder, Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials, Energy & Environmental Science, 4 (2011) 3680-3688.
[3] L.F. Yang, X. Li, X.T. Ma, S. Xiong, P. Liu, Y.Z. Tang, S. Cheng, Y.Y. Hu, M.L. Liu, H.L. Chen, Design of high-performance cathode materials with single-phase pathway for sodium ion batteries: A study on P2-Na-x(LiyMn1-y)O-2 compounds, J. Power Sources, 381 (2018) 171-180.
(Invited) Carbon Fiber-Paper–Supported Carbon Nanofoams As Free-Standing Electrode Architectures for Reversible Sodium-Ion Storage
Authors: Long Jeffrey W. , DeBlock Ryan , Sassin Megan B. , Rolison Debra R. , Hoffmaster Ashley , Ko Jesse S. 
Published: February 2020

Hard (non-graphitizable) carbon has emerged as a prospective charge-storage material for negative electrodes in sodium-ion batteries, yet reported electrochemical performance across this broad category of carbons varies widely. Such discrepancies arise in part due to the multiple distinct sodiation reactions that are possible with disordered carbon electrodes, whereby sodium ions can be stored in defect sites, graphitic layers, and/or micropores depending on the pore–solid architecture, surface chemistry, and solid-state structure of a particular carbon. To address both fundamental questions and practical application in Na-ion batteries, we are investigating carbon nanofoam papers (CNFPs), synthesized by infiltrating the voids of carbon-fiber paper with resorcinol–formaldehyde (R–F) formulations to form porous polymer nanofoam that is subsequently converted to the conductive carbon analog via pyrolysis at 1000°C [1]. When tested as free-standing electrode architectures in Na-ion cells, CNFPs deliver specific capacity >300 mAh g–1 at a 1C rate and >250 mAh g–1 at 10C, with a first-cycle Coulombic efficiency near 85% under galvanostatic operation. The galvanostatic intermittent titration technique (GITT) confirms that Na-ion diffusion is facile in the defect-mediated charge-storage regime. We attribute these favorable properties to the high defect concentration in the disordered R–F-derived carbon domains, the 3D-interconnected porosity within the carbon nanofoam, and the absence of otherwise-necessary binder and conductive additives that are commonly used in conventional powder-composite electrodes. Our results demonstrate the utility of CNFPs as device-ready, self-supported electrodes and advance the design of related carbon materials for next-generation Na-ion batteries.
[1] J.C. Lytle, J.M. Wallace, M.B. Sassin, A.J. Barrow, J.W. Long, J.L. Dysart, C.H. Renninger, M.P. Saunders, N.L. Brandell, and D.R. Rolison, Energy Environ. Sci., 4 (2011) 1913–1925.
Structural Evolution of Solid-State Li2O2 with Reduced Charge Overpotential in Li−O2 Batteries
Authors: Tan Guoqiang , Lu Jun , Chong Lina , Wen Jianguo , Ma Lu , Yuan Yifei , Zeng Xiaoqiao , Li Tao , Wu Tianpin , Liu Cong , Liu Di-Jia , Amine Khalil 
Published: February 2020

Reducing charge-discharge overpotential is helpful to enhance efficiency and cyclability of Li−O2 batteries. In a common non-aqueous Li−O2 cell, the overpotential is largely related to the formation and decomposition processes of solid-state Li2O2. Although several intrinsic properties of Li2O2 have been considered to contribute to the high overpotential, such as the low electrical conductivity, slow dynamics, large particle aggregations, and side-reaction products, et.al,1-4 a fundamental study of specific relationship between overpotential and electrochemical reactions associating with structural evolution of Li2O2 has yet to be undertaken. Besides, the underlying mechanism of the oxygen evolution reaction on charge remains less understood.
To address the above problems, in this work, we proposed a Pt modification strategy to tune cathode architectural to optimize catalytic and electrical properties as well as electrode dynamics. We employed two different approaches of magnetron sputtering and thermal reduction to realize the Pt surface-coating and bulk-doping, respectively. Both could significantly reduce the charge overpotentials of Li−O2 cells with a higher performance from the bulk-doped catalyst. Meanwhile, systematic studies showed an unprecedented relevancy between overpotential and structural evolution of Li2O2, and the Pt nano-composition in the cathode was found to directly affect the formation and decomposition mechanism of Li2O2. Furthermore, we carried out the density functional theory calculations that provided molecular insights into the catalytic role of Pt and Pt3Co nanocrystals (resulting from surface-coating and bulk-coating, respectively) in reducing the charge overpotential.
As a result, the nanoscale bulk-doping approach was demonstrated to be a promising strategy to address the insufficient catalytic and electrical properties and sluggish electrode dynamics of oxygen cathodes for Li−O2 batteries. The exclusive insight into structural evolution of Li2O2 with the reduced charge-discharge overpotential could afford favorable theoretical investigates for further explorations on cathode materials.

Figure 1 Electrochemical discharge/charge profile and corresponding formation and decomposition mechanism of Li2O2 for the Pt bulk-doping catalyst.

References

1 Freunberger S A, et al. Reactions in the rechargeable lithium–O2 battery with alkyl carbonate electrolytes. J.
Am. Chem. Soc., 2011, 133, 8040-8047.
2 Thotiyl M M O, et al. A stable cathode for the aprotic Li–O2 battery. Nat. Mater., 2013, 12, 1050-1056.
3 Chen Y, et al. Charging a Li–O2 battery using a redox mediator. Nat.
Chem., 2013, 5, 489-494.
4 Lim H-D, et al. Rational design of redox mediators for advanced Li–O2 batteries. Nat.
Energy, 2016, 1, 16066.

Figure 1
Lithium Ion Conducting Block Copolymers: Conductivity and Battery Performance
Authors: He Yubin , Min Youn Ji , Liu Nian , Kohl Paul A 
Published: February 2020

Polymeric solid electrolytes are an enabling technology for an all solid-state lithium battery using an intercalation or metal anode. In this study, random and block copolymers with polar functional groups were characterized for use in lithium batteries. The focus of this talk is on the lithium ion conductivity and structure-property relationship of the solid polymer electrolyte.
The block copolymer is synthesized by sequential raft polymerization of different monomers. The first block is poly(acrylate) or poly(styrene), which is imparts sufficient mechanical properties to the polymer. The second block is poly(carbonate) (PC) or polyethylene glycol (PEG) to solvate the lithium ions. Nano-phase separation occurs when the polymer is cast due to differences in polarity between the two blocks. Lithium salts and plasticizer are included in the polymer mixture. The interconnected polycarbonate phase provides ion conducting channels for lithium ion conduction. The mechanical properties of the solid polymer electrolyte are also improved by creating a crosslinking network.
Experimentally, a series of block co-polymers with different molecular weight and block ratio have been synthesized. The chemical structure of the block co-polymers was characterized by NMR and gel permeation chromatography. The nano-phase separation is confirmed by small angle scattering spectroscopy. Li ion conductivity was measured by electrochemical impedance spectroscopy (EIS). The battery performance was tested with Li metal anode and LiFePO4 cathode. The relationship between polymer structure, nano-phase separation and membrane performance will be discussed in this talk.
Metal Phosphide-Embedded Phosphorus-Based Nanocomposite Anode Materials for Rechargeable Batteries
Authors: Kim Sang-Ok 
Published: February 2020

The development of high-performance rechargeable batteries including advanced lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) has been accelerated due to the rapid growth of electric vehicles and stationary large-scale energy storage systems. As one of promising alloying-based anode candidates, elemental phosphorus has attracted much attention among researchers because of its significantly high theoretical specific capacity of 2595 mA h g-1 in both LIBs and SIBs, low-cost, and environmental benignity. However, there are shortcomings such as the large volume change during alloying/dealloying reactions and low conductivity (10-14 S cm-1) of phosphorus, which results in poor cycle performance and slow electrode kinetics. Most approaches aiming at the development of phosphorus-based anode materials have focused on overcoming these difficulties through the utilization of composite structure with nanoscale carbonaceous materials as conductive buffer matrices. While these composites have shown improved cycle and rate performance of phosphorus, they suffer from low initial charge/discharge efficiency and low energy density due to the high carbon content in the structure.
In this work, phosphorus-based nanocomposites containing both metal phosphide structure-reinforcing buffer and carbon network have been synthesized by a simple mechanical ball milling method. Morphological characterization shows that metal phosphide particles are well-mixed with phosphorus and further dispersed in carbon matrix. The resultant phosphorus-based nanocomposites exhibit a significantly improved electrochemical performance compared with amorphous red phosphorus, with a high initial Coulombic efficiency of over 80% in both LIB and SIB systems. Combined structural and electrochemical investigation demostrates that the performance improvement is mainly attributed to the presence of conductive phosphide inclusions that mitigates structural degradation and offers high conductivity.