Publications

2023
Gil Bergman, Ballas, Elad , Gao, Qiang , Nimkar, Amey , Gavriel, Bar , Levi, Mikhael D. , Sharon, Daniel , Malchik, Fyodor , Wang, Xuehang , Shpigel, Netanel , Mandler, Daniel , and Aurbach, Doron . 2023. “Elucidation Of The Charging Mechanisms And The Coupled Structural–Mechanical Behavior Of Ti3C2Tx (Mxenes) Electrodes By In Situ Techniques”. doi:10.1002/aenm.202203154. Abstract
The discovery of the Ti3C2Tx compounds (MXenes) a decade ago opened new research directions and valuable opportunities for high-rate energy storage applications. The unique ability of the MXenes to host various mono- and multivalent cations and their high stability in different electrolyte environments including aqueous, organic, and ionic liquid solutions, promoted the rapid development of advanced MXene-based electrodes for a large variety of applications. Unlike the vast majority of typical intercalation compounds, the electrochemical performance of MXene electrodes is strongly influenced by the presence of co-inserted solvent molecules, which cannot be detected by conventional current/potential electrochemical measurements. Furthermore, the electrochemical insertion of ions into MXene interspaces results in strong coupling with the intercalation-induced structural, dimensional, and viscoelastic changes in the polarized MXene electrodes. To shed light on the charging mechanisms of MXene systems and their associated phenomena, the use of a large variety of real-time monitoring techniques has been proposed in recent years. This review summarizes the most essential findings related to the charging mechanism of Ti3C2Tx electrodes and their potential induced structural and mechanical phenomena obtained by in situ investigations.
Sri Harsha Akella, Bagavathi, Muniyandi , Rosy, , Sharon, Daniel , Ozgur, Capraz , and Noked, Malachi . 2023. “Exploring The Impact Of Lithium Halide-Based Redox Mediators In Suppressing Co 2 Evolution In Li–O 2 Cells”. Journal Of Materials Chemistry A. doi:10.1039/D3TA03002D. Abstract

The graphical abstract depicts that the Li–O 2 cell failure is directly proportional to CO 2 evolution. Cells containing optimal LiBr as redox mediator has significantly suppressed the CO 2 evolution upon prolonged Li–O 2 cycling.

Peter Bennington, Sánchez-Leija, Regina J, Deng, Chuting , Sharon, Daniel , de Pablo, Juan J, Patel, Shrayesh N, and Nealey, Paul F. 2023. “Mixed-Polarity Copolymers Based On Ethylene Oxide And Cyclic Carbonate: Insights Into Li-Ion Solvation And Conductivity”. Macromolecules. doi:10.1021/acs.macromol.3c00540. Abstract
This study investigates the relationship between polarity and ionic conductivity in random and block copolymer electrolytes comprising highly flexible oligo(ethylene oxide) methyl ether methacrylate (OEM) and highly polar but glassy glycerol carbonate methacrylate (GCMA) monomers, blended with either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium triflate. Interestingly, the high polarity of GCMA did not significantly enhance ionic dissociation, and the random copolymers (POEM-r-PGCMA) showed similar or lower ionic conductivities than the POEM homopolymer. Further analysis revealed that Li+ only interacts with OEM and its counterion, not with GCMA. The less-intermixed and weakly phase-separated block copolymer (POEM-b-PGCMA) exhibited even lower conductivities than the random copolymer. Our results suggest that Li+ solvation occurs only in the POEM-rich phase and that the larger PGCMA regions, depleted of Li+, disrupt long-range ion transport. These findings provide valuable insights into the design of polymer electrolytes and how segmental mobility and functional groups with contrasting polarities affect ion transport.
Omer Blumen, Bergman, Gil , Schwatrzman, Keren , Harpaz, Sara , Akella, Sri Harsha, Chae, Munseok S. , Bruchiel-Spanier, Netta , Shpigel, Netanel , and Sharon, Daniel . 2023. “Selection Criteria For Current Collectors For Highly Efficient Anode-Free Zn Batteries”. Journal Of Materials Chemistry A. doi:10.1039/D3TA03766E. Abstract

This work provides comprehensive investigations of reversible zinc metal electrodeposition on various metallic and nonmetallic substrates and describes the main factors influencing the coulombic efficiency of the process.

2022
Bar Gavriel, Bergman, Gil , Turgeman, Meital , Nimkar, Amey , Elias, Yuval , Levi, Mikhael D. , Sharon, Daniel , Shpigel, Netanel , and Aurbach, Doron . 2022. “Aqueous Proton Batteries Based On Acetic Acid Solutions: Mechanistic Insights”. Materials Today Energy, Pp. 101189. doi:10.1016/j.mtener.2022.101189.
Daniel Sharon, Deng, Chuting , Bennington, Peter , Webb, Michael A. , Patel, Shrayesh N. , de Pablo, Juan J. , and Nealey, Paul F. . 2022. “Critical Percolation Threshold For Solvation-Site Connectivity In Polymer Electrolyte Mixtures”. Macromolecules, 55, Pp. 7212-7221. doi:10.1021/acs.macromol.2c00988. Abstract
Poly(ethylene oxide) (PEO)-based polymer electrolytes are often mixed with rigid, nonconductive polymers to improve mechanical strength. The suppressed conductivity of the mixture typically arises from a reduced segmental mobility and a diminished connectivity between conductive PEO sites. To decouple these two mechanisms, we compare transport in symmetric miscible blends and disordered block copolymers (BCP) of PEO and poly(methyl methacrylate) (PMMA). Because the two systems have identical physicochemical properties, differences in their conductivity directly reflect the underlying PEO network connectivity. We find that, at short distances (<5 Å), the Li+ solvation networks are identical for the two systems; however, a distinct variation in the network connectivity arises at length scales between 5 and 10 Å. Specifically, the BCP exhibits a lower connectivity, and therefore a lower conductivity than the blend. A quantitative model is proposed that associates long-range Li+ transport with local miscibility; the concept of network connectivity discussed here could be useful for designing polymer electrolyte systems.
Ran Attias, Dlugatch, Ben , Blumen, Omer , Shwartsman, Keren , Salama, Michal , Shpigel, Netanel , and Sharon, Daniel . 2022. “Determination Of Average Coulombic Efficiency For Rechargeable Magnesium Metal Anodes In Prospective Electrolyte Solutions”. Acs Applied Materials & Interfaces, 14, Pp. 30952-30961. doi:10.1021/acsami.2c08008.
Gil Bergman, Nimkar, Amey , Saha, Arka , Gavriel, Bar , Hen, Meital , Malchik, Fyodor , Fan, Tianju , Tsubery, Merav Nadav , Noked, Malachi , Sharon, Daniel , and Shpigel, Netanel . 2022. “Development Of Electroactive And Stable Current Collectors For Aqueous Batteries”. Journal Of The Electrochemical Society, 169, Pp. 050516. doi:10.1149/1945-7111/ac6c0c. Abstract

The need for low-cost, high-safety batteries for large-scale energy storage applications has sparked a surge in research of rechargeable aqueous batteries. While most research efforts are focused on the development of electrolyte formulations and electrode materials, it appears that the current collector impact on the battery performance is frequently overlooked. Even though the current collector is traditionally thought of as an inactive battery component, it is included in the battery energy density calculations, making its activation desirable. Furthermore, poor current collector selection can cause irreversible side reactions, resulting in rapid cell efficiency decay. Herein we propose a new approach to design current collectors that makes use of anodized Ti. The redox-active anodized Ti significantly improves the overall anode capacity and provides effective inhibition of hydrogen formation on the electrified interface. The use of TiO 2 particles on an anodized Ti current collector in an aqueous electrolyte solution resulted in capacity of 130 mAh g −1 and exceptional capacity retention of 99% after 1000 cycles. Although the concept of active current collectors needs to be refined before it can be implemented in commercial cells, our findings indicate that this approach could be useful for improving overall cell performance without requiring significant changes to its configuration.

Pei Liu, Counihan, Michael J. , Zhu, Yisi , Connell, Justin G. , Sharon, Daniel , Patel, Shrayesh N. , Redfern, Paul C. , Zapol, Peter , Markovic, Nenad M. , Nealey, Paul F. , Curtiss, Larry A. , and Tepavcevic, Sanja . 2022. “Increasing Ionic Conductivity Of Poly(Ethylene Oxide) By Reaction With Metallic Li”. Advanced Energy And Sustainability Research, 3, 1, Pp. 2100142. doi:10.1002/aesr.202100142.
Asmita Dutta, Sathiyan, Krishnamoorthy , Sharon, Daniel , and Borenstein, Arie . 2022. “Laser Induced Incorporation Of Cnts In Graphene Electrodes Improves Flexibility And Conductivity”. Flatchem, 33, Pp. 100378. doi:10.1016/j.flatc.2022.100378.
Asmita Dutta, Sharon, Daniel , Shpigel, Netanel , and Borenstein, Arie . 2022. “Mxenes In Aqueous Electrochemical Energy Systems”. Journal Of Solid State Electrochemistry. doi:10.1007/s10008-022-05244-5.
Amey Nimkar, Chae, Munseok S. , Wee, Shianlin , Bergman, Gil , Gavriel, Bar , Turgeman, Meital , Malchik, Fyodor , Levi, Mikhael D. , Sharon, Daniel , Lukatskaya, Maria R. , Shpigel, Netanel , and Mandler, Daniel . 2022. “What About Manganese? Toward Rocking Chair Aqueous Mn-Ion Batteries”. Acs Energy Letters, Pp. 4161-4167. doi:10.1021/acsenergylett.2c02242.
2021
Ananya Maddegalla, Mukherjee, Ayan , Blázquez, Alberto J, Azaceta, Eneko , Leonet, Olatz , Mainar, Aroa R, Kovalevsky, Aleksey , Sharon, Daniel , Martin, Jean‐Frédéric , Sotta, Dane , Ein‐Eli, Yair , Aurbach, Doron , and Noked, Malachi . 2021. “Az31 Magnesium Alloy Foils As Thin Anodes For Rechargeable Magnesium Batteries”. Chemsuschem, 14, 21, Pp. 4690–4696. doi:10.1002/cssc.202101323. Abstract
In recent decades, rechargeable Mg batteries (RMBs) technologies have attracted much attention because the use of thin Mg foil anodes may enable development of high-energy-density batteries. One of the most critical challenges for RMBs is finding suitable electrolyte solutions that enable efficient and reversible Mg cells operation. Most RMB studies concentrate on the development of novel electrolyte systems, while only few studies have focused on the practical feasibility of using pure metallic Mg as the anode material. Pure Mg metal anodes have been demonstrated to be useful in studying the fundamentals of nonaqueous Mg electrochemistry. However, pure Mg metal may not be suitable for mass production of ultrathin foils (<100 microns) due to its limited ductility. The metals industry overcomes this problem by using ductile Mg alloys. Herein, the feasibility of processing ultrathin Mg anodes in electrochemical cells was demonstrated by using AZ31 Mg alloys (3 % Al; 1 % Zn). Thin-film Mg AZ31 anodes presented reversible Mg dissolution and deposition behavior in complex ethereal Mg electrolytes solutions that was comparable to that of pure Mg foils. Moreover, it was demonstrated that secondary Mg battery prototypes comprising ultrathin AZ31 Mg alloy anodes (≈25 $μ$m thick) and MgxMo6S8 Chevrel-phase cathodes exhibited cycling performance equal to that of similar cells containing thicker pure Mg foil anodes. The possibility of using ultrathin processable Mg metal anodes is an important step in the realization of rechargeable Mg batteries.
Ran Attias, Sharon, Daniel , Goffer, Yosef , and Aurbach, Doron . 2021. “Critical Review On The Unique Interactions And Electroanalytical Challenges Related To Cathodes ‐ Solutions Interfaces In Non‐Aqueous Mg Battery Prototypes”. Chemelectrochem, 8, 17, Pp. 3229–3238. doi:10.1002/celc.202100452.
Sri Harsha Akella, Taragin, Sarah , Wang, Yang , Aviv, Hagit , Kozen, Alexander C, Zysler, Melina , Wang, Longlong , Sharon, Daniel , Lee, Sang Bok , and Noked, Malachi . 2021. “Improvement Of The Electrochemical Performance Of Lini 0.8 Co 0.1 Mn 0.1 O 2 Via Atomic Layer Deposition Of Lithium-Rich Zirconium Phosphate Coatings”. Acs Applied Materials & Interfaces, 13, 51, Pp. 61733–61741. doi:10.1021/acsami.1c16373.
Hannah Dykes, ., Rosy , Sharon, Daniel , Noked, Malachi , and Capraz, Omer Ozgur . 2021. “In Situ Stress Measurements On Thin Film Au Positive Electrode During The First Discharge Of Li-O2 Batteries”. Journal Of The Electrochemical Society. doi:10.1149/1945-7111/ac3937. Abstract
The formation and growth of the Li2O2 discharge product impacts the reversibility of the oxygen evolution and reduction reactions in Li-O2 batteries which may lead to a shorter cycle life. A clear understanding of the surface reactions and the growth mechanism of Li2O2 requires probing dynamic changes on the surface of the positive electrodes in situ during the discharge of a Li-O2 battery. To investigate this, we establish an experimental system by adopting a multi-beam optical sensor (MOS) and developing a custom-made battery cell. First, the accuracy and reliability of the system was demonstrated by analyzing the stress accumulation on the Au negative electrode during Li plating/stripping, and the results were consistent with an earlier single-beam scanning deflectometry report. Then, the Li-O2 battery was discharged in LiNO3 in diglyme electrolyte by applying either linear sweep voltammetry or by applying constant current under an O2 environment. Control experiments in Argon-saturated electrolytes indicate surface stress generation due to charge-induced stress. The stress generation on Au positive electrode is attributed to the formation of Li2O2 reaction products on the Au surface and charge-induced stress.
Daniel Sharon, Bennington, Peter , Webb, Michael A, Deng, Chuting , de Pablo, Juan J. , Patel, Shrayesh N, and Nealey, Paul F. 2021. “Molecular Level Differences In Ionic Solvation And Transport Behavior In Ethylene Oxide-Based Homopolymer And Block Copolymer Electrolytes”. Journal Of The American Chemical Society, 143, 8, Pp. 3180–3190. doi:10.1021/jacs.0c12538. Abstract
Block copolymer electrolytes (BCE) such as polystyrene-block-poly(ethylene oxide) (SEO) blended with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and composed of mechanically robust insulating and rubbery conducting nanodomains are promising solid-state electrolytes for Li batteries. Here, we compare ionic solvation, association, distribution, and conductivity in SEO-LiTFSI BCEs and their homopolymer PEO-LiTFSI analogs toward a fundamental understanding of the maximum in conductivity and transport mechanisms as a function of salt concentration. Ionic conductivity measurements reveal that SEO-LiTFSI and PEO-LiTFSI exhibit similar behaviors up to a Li/EO ratio of 1/12, where roughly half of the available solvation sites in the system are filled, and conductivity is maximized. As the Li/EO ratios increase to 1/5 the conductivity, of the PEO-LiTFSI drops nearly 3-fold, while the conductivity of SEO-LiTFSI remains constant. FTIR spectroscopy reveals that additional Li cations in the homopolymer electrolyte are complexed by additional EO units when the Li/EO ratio exceeds 1/12, while in the BCE, the proportion of complexed and uncomplexed EO units remains constant; Raman spectroscopy data at the same concentrations show that Li cations in the SEO-LiTFSI samples tend to coordinate more to their counteranions. Atomistic-scale molecular dynamics simulations corroborate these results and further show that associated ions tend to segregate to the SEO-LiTFSI domain interfaces. The opportunity for "excess"salt to be sequestered at BCE interfaces results in the retention of an optimum ratio of uncompleted and complexed PEO solvation sites in the middle of the conductive nanodomains of the BCE and maximized conductivity over a broad range of salt concentrations.
Chuting Deng, Webb, Michael A. , Bennington, Peter , Sharon, Daniel , Nealey, Paul F. , Patel, Shrayesh N. , and de Pablo, Juan J. . 2021. “Role Of Molecular Architecture On Ion Transport In Ethylene Oxide-Based Polymer Electrolytes”. Macromolecules, 54, 5, Pp. 2266–2276. doi:10.1021/acs.macromol.0c02424. Abstract
This work aims to develop a detailed mechanistic understanding of the role of a graft polymer architecture on lithium ion (Li+) transport in poly(ethylene oxide)-based polymer electrolytes. Specifically, we compare Li+ transport in poly(ethylene oxide) (PEO) versus poly(oligo oxyethylene methacrylate) (POEM) polymers doped with lithium bis(trifluoromethanesulfonyl) (LiTFSI) salts, using both experimental electrochemical characterization and molecular dynamics (MD) simulations. Our results indicate that POEM exhibits a range of relaxation processes that cannot be interpreted solely in terms of glass-transition temperature (Tg) effects. Due to its side-chain architecture, the segmental relaxation of POEM is nonuniform across ether oxygens (EOs) and shows a more pronounced sensitivity to temperature above Tg compared to PEO. Moreover, POEM also exhibits a nonuniform Li+ coordination behavior, in which Li+ is primarily solvated by two different chains in POEM, compared to a single chain in PEO. Li+ transport in POEM occurs via two events with distinct characteristic times: a fast intrachain hopping along side chains and a slow interchain hopping between side chains. Taken together, the relaxation processes and ion transport mechanisms identified in POEM provide useful insights into design of more effective solid polymer electrolytes.
Peter Bennington, Deng, Chuting , Sharon, Daniel , Webb, Michael A. , de Pablo, Juan J. , Nealey, Paul F. , and Patel, Shrayesh N. . 2021. “Role Of Solvation Site Segmental Dynamics On Ion Transport In Ethylene-Oxide Based Side-Chain Polymer Electrolytes”. Journal Of Materials Chemistry A, 9, 15, Pp. 9937–9951. doi:10.1039/D1TA00899D. Abstract
Ionic conductivity is governed primarily by the segmental mobility of the side-chain ethylene oxide units which form effective solvation sites, rather than system-wide dynamics.
Sankalpita Chakrabarty, Blázquez, J. Alberto , Sharabani, Tali , Maddegalla, Ananya , Leonet, Olatz , Urdampilleta, Idoia , Sharon, Daniel , Noked, Malachi , and Mukherjee, Ayan . 2021. “Stability Of Current Collectors Against Corrosion In Apc Electrolyte For Rechargeable Mg Battery”. Journal Of The Electrochemical Society, 168, 8, Pp. 080526. doi:10.1149/1945-7111/ac1cc8.

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