Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy
Anno: 2024
Rivista: ENERGY STORAGE MATERIALS
Autori/autrici: Wang, J.; Liu, H.; Zhang, J.; Xiao, Q.; Wang, C.; Zhang, Y.; Liu, M.; Kang, Q.; Jia, L.; Wang, D.; Li, Q.; Duan, W.; Adenusi, H.; Passerini, S.; Zhang, Y.; Lin, H.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330836
Citazioni:
Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy / Wang, J.; Liu, H.; Zhang, J.; Xiao, Q.; Wang, C.; Zhang, Y.; Liu, M.; Kang, Q.; Jia, L.; Wang, D.; Li, Q.; Duan, W.; Adenusi, H.; Passerini, S.; Zhang, Y.; Lin, H.. - In: ENERGY STORAGE MATERIALS. - ISSN 2405-8297. - 67:(2024). [10.1016/j.ensm.2024.103289]
Abstract:
Understanding of interfacial Li+ solvation shell structures and dynamic evolution at the electrode/electrolyte interface is requisite for developing high-energy-density Li batteries. Herein, the reorganization of Li+ solvation shell at the sulfur/electrolyte interface along with the presence of a tr...ace amount of lithium polysulfides is verified by in-situ sum frequency generation (SFG) spectroscopy together with density functional theory (DFT) calculations. Both the spectroelectrochemical and DFT calculation results reveal a strongly competitive anion adsorption of the polysulfide anion additive against the pristine electrolyte anion on the sulfur cathode surface, reorganizing the interfacial local solvation shell structure facilitating rapid Li ion transfer and conduction. Meanwhile, the evolution of the SFG signals along with the discharging/charging cycle exhibits improved reversibility, indicating the transformation of the inner Helmholtz plane layer into a stable molecular-layer polysulfide interphase rather than a dynamic diffusion layer. Consequently, applications in practical Li-S batteries reveal the capacity and cycling stability of the corresponding cells are significantly enhanced. Our work provides a methodology using in-situ SFG for probing solvation reorganization of charge carriers at electrochemical interfaces.
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Fast interfacial electrocatalytic desolvation enabling low-temperature and long-cycle-life aqueous Zn batteries
Anno: 2024
Rivista: INFOMAT
Autori/autrici: Wang, Jian; Hu, Hongfei; Jia, Lujie; Zhang, Jing; Zhuang, Quan; Li, Linge; Zhang, Yongzheng; Wang, Dong; Guan, Qinghua; Hu, Huimin; Liu, Meinan; Zhan, Liang; Adenusi, Henry; Passerini, Stefano; Lin, Hongzhen
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/333059
Citazioni:
Fast interfacial electrocatalytic desolvation enabling low-temperature and long-cycle-life aqueous Zn batteries / Wang, Jian; Hu, Hongfei; Jia, Lujie; Zhang, Jing; Zhuang, Quan; Li, Linge; Zhang, Yongzheng; Wang, Dong; Guan, Qinghua; Hu, Huimin; Liu, Meinan; Zhan, Liang; Adenusi, Henry; Passerini, Stefano; Lin, Hongzhen. - In: INFOMAT. - ISSN 2567-3165. - 6:7(2024). [10.1002/INF2.12558]
Abstract:
Low-temperature zinc batteries (LT-ZIBs) based on aqueous electrolytes show great promise for practical applications owing to their natural resource abundance and low cost. However, they suffer from sluggish kinetics with elevated energy barriers due to the dissociation of bulky Zn(H2O)(6)(2+) solva...tion structure and free Zn2+ diffusion, resulting in unsatisfactory lifespan and performance. Herein, dissimilar to solvation shell tuning or layer spacing enlargement engineering, delocalized electrons in cathode through constructing intrinsic defect engineering is proposed to achieve a rapid electrocatalytic desolvation to obtain free Zn2+ for insertion/extraction. As revealed by density functional theory calculations and interfacial spectroscopic characterizations, the intrinsic delocalized electron distribution propels the Zn(H2O)(6)(2+) dissociation, forming a reversible interphase and facilitating Zn2+ diffusion across the electrolyte/cathode interface. The as-fabricated oxygen defect-rich V2O5 on hierarchical porous carbon (ODVO@HPC) electrode exhibits high capacity robustness from 25 to -20 degrees C. Operating at -20 degrees C, the ODVO@HPC delivers 191 mAh g(-1) at 50 A g(-1) and lasts for 50 000 cycles at 10 A g(-1), significantly enhancing the power density and lifespan under low-temperature environments in comparison to previous reports. Even with areal mass loading of similar to 13 mg cm(-2), both coin cells and pouch batteries maintain excellent stability and areal capacities, realizing practical high-performance LT-ZIBs.
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Superionicity by design: high proton conductivity in a fluorine-free protic ionic liquid
Anno: 2024
Rivista: JOURNAL OF MATERIALS CHEMISTRY. A
Autori/autrici: Schutz, H. M.; Nejrotti, S.; Adenusi, H.; Mariani, A.; Bodo, E.; Bonomo, M.; Innocenti, A.; Barolo, C.; Gao, X.; Passerini, S.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/333060
Citazioni:
Superionicity by design: high proton conductivity in a fluorine-free protic ionic liquid / Schutz, H. M.; Nejrotti, S.; Adenusi, H.; Mariani, A.; Bodo, E.; Bonomo, M.; Innocenti, A.; Barolo, C.; Gao, X.; Passerini, S.. - In: JOURNAL OF MATERIALS CHEMISTRY. A. - ISSN 2050-7488. - 12:29(2024), pp. 18412-18422. [10.1039/d4ta02880e]
Abstract:
In this study, the protic ionic liquid N,N-diethyl-3-sulfopropan-1-ammonium hydrogen methanedisulfonate is synthesized and characterized with the aim of elucidating its transport properties. A unique feature of this ionic liquid are the exchangeable acidic protons present on the anion and the cation..., both of which contain low proton affinity sulfonic groups. The pronounced superionicity of this liquid, highlighted in the Walden-plot (ΔW > 0.8), indicates the decoupling of the conductivity from ionic diffusion. To explicate this enhanced proton mobility, the diffusion coefficients of the protons were measured by Pulsed-Field Gradient Spin-Echo NMR experiments at different temperatures. Below 373 K the diffusion coefficients of the cationic and anionic exchangeable protons are comparable with the ones of the other protons of the respective ions, indicating a vehicular transport mechanism. However, in the temperature range 383-413 K the diffusion coefficient of one of the exchangeable protons exceeds the diffusion of both ions by an unprecedented factor between 2 and 3. This temperature-induced switch in the proton transport mechanism is the result of a mixed-ion proton-transfer chain, as also supported by computational simulations. Both experimental and theoretical findings suggest the existence of a Grotthuss(-like) proton transport mechanism at high temperature in this system.
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Silicon-Containing Anodes for High-Energy Density Lithium-Ion Batteries
Anno: 2023
Rivista: MEETING ABSTRACTS
Autori/autrici: Gebresilassie Eshetu, Gebrekidan; Zhang, Heng; Judez, Xabier; Adenusi, Henry; Armand, Michel; Passerini, Stefano; Figgemeier, Egbert
Lingua: ENG
Classificazione IRIS: 4.2 Abstract in Atti di convegno
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330903
Citazioni:
Silicon-Containing Anodes for High-Energy Density Lithium-Ion Batteries / Gebresilassie Eshetu, Gebrekidan; Zhang, Heng; Judez, Xabier; Adenusi, Henry; Armand, Michel; Passerini, Stefano; Figgemeier, Egbert. - In: MEETING ABSTRACTS. - ISSN 2151-2043. - MA2023-01:(2023), pp. 522-522. [10.1149/MA2023-012522mtgabs]

Assessing n-type organic materials for lithium batteries: A techno-economic review
Anno: 2023
Rivista: INFOMAT
Autori/autrici: Innocenti, A.; Adenusi, H.; Passerini, S.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330848
Citazioni:
Assessing n-type organic materials for lithium batteries: A techno-economic review / Innocenti, A.; Adenusi, H.; Passerini, S.. - In: INFOMAT. - ISSN 2567-3165. - 5:11(2023). [10.1002/inf2.12480]
Abstract:
The high demand for critical minerals such as lithium, copper, nickel, and cobalt, required for lithium-ion batteries, has raised questions regarding the feasibility of maintaining a steady and affordable supply of raw materials for their production. In the last years, researchers have shifted their... attention toward organic materials, which are potentially more widely available, affordable, and sustainable due to the ubiquitous presence of the constituent organic elements. The n-type materials have a redox mechanism analogous to that of lithium-ion cathodes and anodes, hence they are suitable for a meaningful comparison with the state-of-the-art technology. While many reviews have evaluated the properties of organic materials at the material or electrode level, herein, the properties of n-type organic materials are assessed in a complex system, such as a full battery, to evaluate the feasibility and performance of these materials in commercial-scale battery systems. The most relevant cathode materials for organic batteries are reviewed, and a detailed cost and performance analysis of n-type material-based battery packs using the BatPaC 5.0 software is presented. The analysis considers the influence of electrode design choices, such as the conductive carbon content, active material mass loading, and electrode density, on energy density and cost. The potential of n-type organic materials as a low-cost and sustainable solution for energy storage applications is highlighted, while emphasizing the need for further advancements of organic materials for energy storage applications.
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Bioactivity of the cannabigerol cannabinoid and its analogues – the role of 3-dimensional conformation
Anno: 2023
Rivista: ORGANIC & BIOMOLECULAR CHEMISTRY
Autori/autrici: Salha, Mohammed; Adenusi, Henry; Dupuis, John H.; Bodo, Enrico; Botta, Bruno; Mckenzie, Iain; Yada, Rickey Y.; Farrar, David H.; Magolan, Jakob; Tian, Kun V.; Chass, Gregory A.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330830
Citazioni:
Bioactivity of the cannabigerol cannabinoid and its analogues – the role of 3-dimensional conformation / Salha, Mohammed; Adenusi, Henry; Dupuis, John H.; Bodo, Enrico; Botta, Bruno; Mckenzie, Iain; Yada, Rickey Y.; Farrar, David H.; Magolan, Jakob; Tian, Kun V.; Chass, Gregory A.. - In: ORGANIC & BIOMOLECULAR CHEMISTRY. - ISSN 1477-0520. - 21:22(2023), pp. 4683-4693. [10.1039/D3OB00383C]
Abstract:
Cannabinoids are naturally occurring bioactive compounds with the potential to help treat chronic illnesses including epilepsy, Parkinson's disease, dementia and multiple sclerosis. Their general structures and efficient syntheses are well documented in the literature, yet their quantitative structu...re-activity relationships (QSARs), particularly 3-dimensional (3-D) conformation-specific bioactivities, are not fully resolved. Cannabigerol (CBG), an antibacterial precursor molecule for the most abundant phytocannabinoids, was characterised herein using density functional theory (DFT), together with selected analogues, to ascertain the influence of the 3D structure on their activity and stability. Results showed that the CBG family's geranyl chains tend to coil around the central phenol ring while its alkyl side-chains form H-bonds with the para-substituted hydroxyl groups as well as CHMIDLINE HORIZONTAL ELLIPSIS pi interactions with the aromatic density of the ring itself, among other interactions. Although weakly polar, these interactions are structurally and dynamically influential, effectively 'stapling' the ends of the chains to the central ring structure. Molecular docking of the differing 3-D poses of CBG to cytochrome P450 3A4 resulted in lowered inhibitory action by the coiled conformers, relative to their fully-extended counterparts, helping explain the trends in the inhibition of the metabolic activity of the CYP450 3A4. The approach detailed herein represents an effective method for the characterisation of other bioactive molecules, towards improved understanding of their QSARs and in guiding the rational design and synthesis of related compounds.
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Electrolyte Strategies Facilitating Anion-Derived Solid-Electrolyte Interphases for Aqueous Zinc–Metal Batteries
Anno: 2023
Rivista: SMALL METHODS
Autori/autrici: Li, H.; Chen, Z.; Zheng, L.; Wang, J.; Adenusi, H.; Passerini, S.; Zhang, H.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330838
Citazioni:
Electrolyte Strategies Facilitating Anion-Derived Solid-Electrolyte Interphases for Aqueous Zinc–Metal Batteries / Li, H.; Chen, Z.; Zheng, L.; Wang, J.; Adenusi, H.; Passerini, S.; Zhang, H.. - In: SMALL METHODS. - ISSN 2366-9608. - 8:6(2023). [10.1002/smtd.202300554]
Abstract:
Rechargeable aqueous zinc–metal batteries (AZBs) are a promising complimentary technology to the existing lithium-ion batteries and the re-emerging lithium–metal batteries to satisfy the increasing demands on energy storage. Despite considerable progress achieved in the past years, the fundament...al understanding of the solid-electrolyte interphase (SEI) formation and how its composition influences the SEI properties are limited. This review highlights the functionalities of anion-tuned SEI on the reversibility of zinc–metal anode, with a specific emphasis on new structural insights obtained through advanced characterizations and computational techniques. Recent efforts in terms of key variables that govern the interfacial behaviors to improve the long-term stability of zinc anode, i.e., Coulombic efficiency, plating morphology, dendrite formation, and side-reactions, are comprehensively reviewed. Lastly, the remaining challenges and future perspectives are presented, providing insights into the rational design of practical high-performance AZBs.
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Interfacial “Single-Atom-in-Defects” Catalysts Accelerating Li+ Desolvation Kinetics for Long-Lifespan Lithium-Metal Batteries
Anno: 2023
Rivista: ADVANCED MATERIALS
Autori/autrici: Wang, J.; Zhang, J.; Wu, J.; Huang, M.; Jia, L.; Li, L.; Zhang, Y.; Hu, H.; Liu, F.; Guan, Q.; Liu, M.; Adenusi, H.; Lin, H.; Passerini, S.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330849
Citazioni:
Interfacial “Single-Atom-in-Defects” Catalysts Accelerating Li+ Desolvation Kinetics for Long-Lifespan Lithium-Metal Batteries / Wang, J.; Zhang, J.; Wu, J.; Huang, M.; Jia, L.; Li, L.; Zhang, Y.; Hu, H.; Liu, F.; Guan, Q.; Liu, M.; Adenusi, H.; Lin, H.; Passerini, S.. - In: ADVANCED MATERIALS. - ISSN 0935-9648. - 35:39(2023). [10.1002/adma.202302828]
Abstract:
The lithium-metal anode is a promising candidate for realizing high-energy-density batteries owing to its high capacity and low potential. However, several rate-limiting kinetic obstacles, such as the desolvation of Li+ solvation structure to liberate Li+, Li0 nucleation, and atom diffusion, cause h...eterogeneous spatial Li-ion distribution and fractal plating morphology with dendrite formation, leading to low Coulombic efficiency and depressive electrochemical stability. Herein, differing from pore sieving effect or electrolyte engineering, atomic iron anchors to cation vacancy-rich Co1−xS embedded in 3D porous carbon (SAFe/CVRCS@3DPC) is proposed and demonstrated as catalytic kinetic promoters. Numerous free Li ions are electrocatalytically dissociated from the Li+ solvation complex structure for uniform lateral diffusion by reducing desolvation and diffusion barriers via SAFe/CVRCS@3DPC, realizing smooth dendrite-free Li morphologies, as comprehensively understood by combined in situ/ex situ characterizations. Encouraged by SAFe/CVRCS@3DPC catalytic promotor, the modified Li-metal anodes achieve smooth plating with a long lifespan (1600 h) and high Coulombic efficiency without any dendrite formation. Paired with the LiFePO4 cathode, the full cell (10.7 mg cm−2) stabilizes a capacity retention of 90.3% after 300 cycles at 0.5 C, signifying the feasibility of using interfacial catalysts for modulating Li behaviors toward practical applications.
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Lithium Batteries and the Solid Electrolyte Interphase (SEI)—Progress and Outlook
Anno: 2023
Rivista: ADVANCED ENERGY MATERIALS
Autori/autrici: Adenusi, H.; Chass, G. A.; Passerini, S.; Tian, K. V.; Chen, G.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330847
Citazioni:
Lithium Batteries and the Solid Electrolyte Interphase (SEI)—Progress and Outlook / Adenusi, H.; Chass, G. A.; Passerini, S.; Tian, K. V.; Chen, G.. - In: ADVANCED ENERGY MATERIALS. - ISSN 1614-6832. - 13:10(2023). [10.1002/aenm.202203307]
Abstract:
Interfacial dynamics within chemical systems such as electron and ion transport processes have relevance in the rational optimization of electrochemical energy storage materials and devices. Evolving the understanding of fundamental electrochemistry at interfaces would also help in the understanding... of relevant phenomena in biological, microbial, pharmaceutical, electronic, and photonic systems. In lithium-ion batteries, the electrochemical instability of the electrolyte and its ensuing reactive decomposition proceeds at the anode surface within the Helmholtz double layer resulting in a buildup of the reductive products, forming the solid electrolyte interphase (SEI). This review summarizes relevant aspects of the SEI including formation, composition, dynamic structure, and reaction mechanisms, focusing primarily on the graphite anode with insights into the lithium metal anode. Furthermore, the influence of the electrolyte and electrode materials on SEI structure and properties is discussed. An update is also presented on state-of-the-art approaches to quantitatively characterize the structure and changing properties of the SEI. Lastly, a framework evaluating the standing problems and future research directions including feasible computational, machine learning, and experimental approaches are outlined.
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Locally Concentrated Ionic Liquid Electrolytes for Lithium-Metal Batteries
Anno: 2023
Rivista: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION
Autori/autrici: Liu, X.; Mariani, A.; Adenusi, H.; Passerini, S.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330834
Citazioni:
Locally Concentrated Ionic Liquid Electrolytes for Lithium-Metal Batteries / Liu, X.; Mariani, A.; Adenusi, H.; Passerini, S.. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 62:17(2023). [10.1002/anie.202219318]
Abstract:
Non-flammable ionic liquid electrolytes (ILEs) are well-known candidates for safer and long-lifespan lithium metal batteries (LMBs). However, the high viscosity and insufficient Li+ transport limit their practical application. Recently, non-solvating and low-viscosity co-solvents diluting ILEs witho...ut affecting the local Li+ solvation structure are employed to solve these problems. The diluted electrolytes, i.e., locally concentrated ionic liquid electrolytes (LCILEs), exhibiting lower viscosity, faster Li+ transport, and enhanced compatibility toward lithium metal anodes, are feasible options for the next-generation high-energy-density LMBs. Herein, the progress of the recently developed LCILEs are summarised, including their physicochemical properties, solution structures, and applications in LMBs with a variety of high-energy cathode materials. Lastly, a perspective on the future research directions of LCILEs to further understanding and achieve improved cell performances is outlined.
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Could potassium-ion batteries become a competitive technology?
Anno: 2023
Rivista: ENERGY MATERIALS
Autori/autrici: Zarrabeitia, Maider; Carretero-Gonzalez, Javier; Leskes, Michal; Adenusi, Henry; Iliev, Boyan; Schubert, Thomas J. S.; Passerini, Stefano; Castillo-Martinez, Elizabeth
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330842
Citazioni:
Could potassium-ion batteries become a competitive technology? / Zarrabeitia, Maider; Carretero-Gonzalez, Javier; Leskes, Michal; Adenusi, Henry; Iliev, Boyan; Schubert, Thomas J. S.; Passerini, Stefano; Castillo-Martinez, Elizabeth. - In: ENERGY MATERIALS. - ISSN 2770-5900. - 3:6(2023). [10.20517/ENERGYMATER.2023.41]
Abstract:
Potassium-ion batteries (PIBs) have attracted significant attention as a complement to lithium-ion and sodium-ion batteries (SIBs). PIBs can theoretically provide higher specific energy and power density than SIBs due to lower standard electrode potential of K/K+ and faster K+ ion diffusion, maintai...ning the benefits of low-cost and sustainability. However, research on PIBs is in its infancy; therefore, further efforts are necessary to enhance their performance and position them as a competitive technology. In this perspective, the remaining challenges and possible strategies to advance the development of PIBs are presented.
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Ionic liquids and their derivatives for lithium batteries: role, design strategy, and perspectives
Anno: 2023
Rivista: ENERGY MATERIALS
Autori/autrici: Palluzzi, Matteo; Tsurumaki, Akiko; Adenusi, Henry; Navarra, Maria Assunta; Passerini, Stefano
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330851
Citazioni:
Ionic liquids and their derivatives for lithium batteries: role, design strategy, and perspectives / Palluzzi, Matteo; Tsurumaki, Akiko; Adenusi, Henry; Navarra, Maria Assunta; Passerini, Stefano. - In: ENERGY MATERIALS. - ISSN 2770-5900. - 3:6(2023). [10.20517/ENERGYMATER.2023.48]
Abstract:
Lithium-ion batteries (LIBs) are the predominant power source for portable electronic devices, and in recent years, their use has extended to higher-energy and larger devices. However, to satisfy the stringent requirements of safety and energy density, further material advancements are required. Due... to the inherent flammability and incompatibility of organic solvent-based liquid electrolytes with materials utilized in high energy devices, it is necessary to transition to alternative conductive mediums. The focus is shifting from molecular materials to a class of materials based on ions, including ionic liquids (ILs) and their derivatives such as zwitterionic ILs, polymerized ILs, and solvated ILs, which possess high levels of safety, stability, compatibility, and the ability to rationally design ILs for specific applications. Ion design is crucial to achieve superior control of electrode/electrolyte interphases (EEIs) both on anode and cathode surfaces to realize safer and higher-energy lithium-metal batteries (LMBs). This review summarizes the different uses of ILs in electrolytes (both liquid and solids) for LMBs, reporting the most promising results obtained during the last years and highlighting their role in the formation of suitable EEIs. Furthermore, a discussion on the use of deep-eutectic solvents is also provided, which is a class of material with similar properties to ILs and an important alternative from the viewpoint of sustainability. Lastly, future prospects for the optimization of IL-based electrolytes are summarized, ranging from the functional design of ionic structures to the realization of nanophases with specific features.
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Quasi-solid-state electrolytes - strategy towards stabilising Li|inorganic solid electrolyte interfaces in solid-state Li metal batteries
Anno: 2023
Rivista: ENERGY MATERIALS
Autori/autrici: Mazzapioda, Lucia; Tsurumaki, Akiko; Di Donato, Graziano; Adenusi, Henry; Assunta Navarra, Maria; Passerini, Stefano
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330840
Citazioni:
Quasi-solid-state electrolytes - strategy towards stabilising Li|inorganic solid electrolyte interfaces in solid-state Li metal batteries / Mazzapioda, Lucia; Tsurumaki, Akiko; Di Donato, Graziano; Adenusi, Henry; Assunta Navarra, Maria; Passerini, Stefano. - In: ENERGY MATERIALS. - ISSN 2770-5900. - 3:2(2023). [10.20517/energymater.2023.03]
Abstract:
Solid-state batteries (SSBs) based on inorganic solid electrolytes (ISEs) are considered promising candidates for enhancing the energy density and the safety of next-generation rechargeable lithium batteries. However, their practical application is frequently hampered by the high resistance arising ...at the Li metal anode/ISE interface. Herein, a review of the conventional solid-state electrolytes (SSEs) the recent research on quasi-solid-state battery (QSSB) approaches to overcome the issues of the state-of-the-art SSBs is reported. The feasibility of ionic liquid (IL)-based interlayers to improve ISE/Li metal wetting and enhance charge transfer at solid electrolyte interfaces with both positive and lithium metal electrodes is presented together with a novel generation of IL-containing quasi-solid-state-electrolytes (QSSEs), offering favourable features. The opportunities and challenges of QSSE for the development of high energy and high safety quasi-solid-state lithium metal batteries (QSSLMBs) are also discussed.
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Advances and issues in developing intercalation graphite cathodes for aqueous batteries
Anno: 2022
Rivista: MATERIALS TODAY
Autori/autrici: Zhang, H.; Guo, G.; Adenusi, H.; Qin, B.; Li, H.; Passerini, S.; Huang, W.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330839
Citazioni:
Advances and issues in developing intercalation graphite cathodes for aqueous batteries / Zhang, H.; Guo, G.; Adenusi, H.; Qin, B.; Li, H.; Passerini, S.; Huang, W.. - In: MATERIALS TODAY. - ISSN 1369-7021. - 53:(2022), pp. 162-172. [10.1016/j.mattod.2022.01.020]
Abstract:
Aqueous rechargeable batteries offer a safe alternative for electrochemical energy storage, integrating cost-efficiency and energy density to meet the demand for stationary applications. Recent efforts have focused on the improvement of electrode materials in aqueous electrolytes, particularly the c...ycle life and energy reliability of batteries. The anion intercalation chemistry in graphite could be an alternative cathode candidate, often requiring an upper cut-off potential above 4.5 V vs. Li+/Li. Such a potential readily exceeds the electrochemical stability windows of water-based electrolytes. Herein, we provide a progress report and critical comment on the reversible intercalation chemistry in graphite compounds, i.e., anion and halogen intercalations, for the development of economical, high-energy aqueous rechargeable batteries. In addition, this review focuses on the charge carrier species, their charge storage mechanisms and battery configurations, aiming to provide solutions to solve the remaining key challenges for aqueous batteries.
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Toward Dendrite-Free Metallic Lithium Anodes: From Structural Design to Optimal Electrochemical Diffusion Kinetics
Anno: 2022
Rivista: ACS NANO
Autori/autrici: Wang, J.; Li, L.; Hu, H.; Hu, H.; Guan, Q.; Huang, M.; Jia, L.; Adenusi, H.; Tian, K. V.; Zhang, J.; Passerini, S.; Lin, H.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330850
Citazioni:
Toward Dendrite-Free Metallic Lithium Anodes: From Structural Design to Optimal Electrochemical Diffusion Kinetics / Wang, J.; Li, L.; Hu, H.; Hu, H.; Guan, Q.; Huang, M.; Jia, L.; Adenusi, H.; Tian, K. V.; Zhang, J.; Passerini, S.; Lin, H.. - In: ACS NANO. - ISSN 1936-0851. - 16:11(2022), pp. 17729-17760. [10.1021/acsnano.2c08480]
Abstract:
Lithium metal anodes are ideal for realizing high-energy-density batteries owing to their advantages, namely high capacity and low reduction potentials. However, the utilization of lithium anodes is restricted by the detrimental lithium dendrite formation, repeated formation and fracturing of the so...lid electrolyte interphase (SEI), and large volume expansion, resulting in severe "dead lithium"and subsequent short circuiting. Currently, the researches are principally focused on inhibition of dendrite formation toward extending and maintaining battery lifespans. Herein, we summarize the strategies employed in interfacial engineering and current-collector host designs as well as the emerging electrochemical catalytic methods for evolving-accelerating-ameliorating lithium ion/atom diffusion processes. First, strategies based on the fabrication of robust SEIs are reviewed from the aspects of compositional constituents including inorganic, organic, and hybrid SEI layers derived from electrolyte additives or artificial pretreatments. Second, the summary and discussion are presented for metallic and carbon-based three-dimensional current collectors serving as lithium hosts, including their functionality in decreasing local deposition current density and the effect of introducing lithiophilic sites. Third, we assess the recent advances in exploring alloy compounds and atomic metal catalysts to accelerate the lateral lithium ion/atom diffusion kinetics to average the spatial lithium distribution for smooth plating. Finally, the opportunities and challenges of metallic lithium anodes are presented, providing insights into the modulation of diffusion kinetics toward achieving dendrite-free lithium metal batteries.
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Electrolyte Measures to Prevent Polysulfide Shuttle in Lithium-Sulfur Batteries
Anno: 2022
Rivista: BATTERIES & SUPERCAPS
Autori/autrici: Di Donato, G.; Ates, T.; Adenusi, H.; Varzi, A.; Navarra, M. A.; Passerini, S.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330831
Citazioni:
Electrolyte Measures to Prevent Polysulfide Shuttle in Lithium-Sulfur Batteries / Di Donato, G.; Ates, T.; Adenusi, H.; Varzi, A.; Navarra, M. A.; Passerini, S.. - In: BATTERIES & SUPERCAPS. - ISSN 2566-6223. - 5:7(2022). [10.1002/batt.202200097]
Abstract:
Lithium-sulfur (Li−S) batteries are recognized as one of the most promising technologies with the potential to become the next-generation batteries. However, to ensure Li−S batteries reach commercialization, complex challenges remain, among which the tailoring of an appropriate electrolyte is th...e most important. This review discusses the role of electrolytes in Li−S batteries, focusing on the main issues and solutions for the shuttle mechanism of polysulfides and the instability of the interface with lithium metal. Herein, we present a background on Li−S chemistry followed by the state-of-the-art electrolytes highlighting the different strategies undertaken with liquid and solid electrolytes.
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Demixing the miscible liquids: toward biphasic battery electrolytes based on the kosmotropic effect
Anno: 2022
Rivista: ENERGY & ENVIRONMENTAL SCIENCE
Autori/autrici: Kim, W. -Y.; Kim, H. -I.; Lee, K. M.; Shin, E.; Liu, X.; Moon, H.; Adenusi, H.; Passerini, S.; Kwak, S. K.; Lee, S. -Y.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330833
Citazioni:
Demixing the miscible liquids: toward biphasic battery electrolytes based on the kosmotropic effect / Kim, W. -Y.; Kim, H. -I.; Lee, K. M.; Shin, E.; Liu, X.; Moon, H.; Adenusi, H.; Passerini, S.; Kwak, S. K.; Lee, S. -Y.. - In: ENERGY & ENVIRONMENTAL SCIENCE. - ISSN 1754-5692. - 15:12(2022), pp. 5217-5228. [10.1039/d2ee03077b]
Abstract:
Exploring new electrolyte chemistry beyond conventional single-phase battery electrolytes is needed to fulfill the heterogeneous requirements of anodes and cathodes. Here, we report a biphasic liquid electrolyte (BLE) based on the kosmotropic effect. The key underlying technology for the BLE is phas...e separation of its electrolyte couples using a principle of “demixing the miscible liquids”. Kosmotropic/chaotropic anions affect the ion coordination structures and the intermolecular interactions of electrolyte couples, enabling on-demand control of their immiscibility/miscibility. Despite the intrinsic miscibility of water (in aqueous electrolytes) and acetonitrile (in nonaqueous electrolytes), the structural change of the aqueous electrolyte induced by kosmotropic anions allows demixing with the nonaqueous electrolyte. The resultant BLE facilitates redox kinetics at cathodes and Zn plating/stripping cyclability at anodes. Consequently, the BLE enables Zn-metal full cells to exhibit a long cyclability (86.6% retention after 3500 cycles). Moreover, Zn anode-free full cells with the BLE exhibit a higher energy density (183 W h kg−1) than previously reported Zn batteries.
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Production of high-energy Li-ion batteries comprising silicon-containing anodes and insertion-type cathodes
Anno: 2021
Rivista: NATURE COMMUNICATIONS
Autori/autrici: Eshetu, G. G.; Zhang, H.; Judez, X.; Adenusi, H.; Armand, M.; Passerini, S.; Figgemeier, E.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330837
Citazioni:
Production of high-energy Li-ion batteries comprising silicon-containing anodes and insertion-type cathodes / Eshetu, G. G.; Zhang, H.; Judez, X.; Adenusi, H.; Armand, M.; Passerini, S.; Figgemeier, E.. - In: NATURE COMMUNICATIONS. - ISSN 2041-1723. - 12:1(2021). [10.1038/s41467-021-25334-8]
Abstract:
Rechargeable Li-based battery technologies utilising silicon, silicon-based, and Si-derivative anodes coupled with high-capacity/high-voltage insertion-type cathodes have reaped significant interest from both academic and industrial sectors. This stems from their practically achievable energy densit...y, offering a new avenue towards the mass-market adoption of electric vehicles and renewable energy sources. Nevertheless, such high-energy systems are limited by their complex chemistry and intrinsic drawbacks. From this perspective, we present the progress, current status, prevailing challenges and mitigating strategies of Li-based battery systems comprising silicon-containing anodes and insertion-type cathodes. This is accompanied by an assessment of their potential to meet the targets for evolving volume- and weight-sensitive applications such as electro-mobility.
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Hydrogen bonding in biocompatible ionic liquids: An ab-initio characterization of dimeric interactions
Anno: 2021
Rivista: ELECTRONIC STRUCTURE
Autori/autrici: Donne, A. L.; Adenusi, H.; Porcelli, F.; Bodo, E.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330844
Citazioni:
Hydrogen bonding in biocompatible ionic liquids: An ab-initio characterization of dimeric interactions / Donne, A. L.; Adenusi, H.; Porcelli, F.; Bodo, E.. - In: ELECTRONIC STRUCTURE. - ISSN 2516-1075. - 3:2(2021). [10.1088/2516-1075/abfd21]
Abstract:
We present here an analysis of the electronic structure of like-charge dimers that occur in a class of protic ionic materials based on the use of amino and phosphonic acids anions. Some of these materials have emerged in recent years as a possible replacement of first-generation ionic liquids becaus...e of their greater biocompatibility, biodegradability and the lower costs of their preparation. At the moment, these materials have eluded a simple and straightforward correlation between their bulk properties and the structure of their molecular components. It has been shown in recent years that part of the complications arises because the anions show an unexpected degree of spatial organization induced by hydrogen bonds. Here we elaborate some of our recent results from molecular dynamics calculations in the view of new accurate electronic structure calculations to characterize the molecular interactions of the molecular partners within the liquid.
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Theoretical insights into the structure of the aminotris(methylenephosphonic acid) (ATMP) anion: A possible partner for conducting ionic media
Anno: 2020
Rivista: SYMMETRY
Autori/autrici: Adenusi, H.; Chass, G.; Bodo, E.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330846
Citazioni:
Theoretical insights into the structure of the aminotris(methylenephosphonic acid) (ATMP) anion: A possible partner for conducting ionic media / Adenusi, H.; Chass, G.; Bodo, E.. - In: SYMMETRY. - ISSN 2073-8994. - 12:6(2020). [10.3390/SYM12060920]
Abstract:
We present a computational characterisation of Aminotris(methylenephosphonic acid) (ATMP) and its potential use as an anionic partner for conductive ionic liquids (ILs). We argue that for an IL to be a good candidate for a conducting medium, two conditions must be fulfilled: (i) the charge must be t...ransported by light carriers; and (ii) the system must maintain a high degree of ionisation. The result trends presented herein show that there are molecular ion combinations that do comply with these two criteria, regardless of the specific system used. ATMP is a symmetric molecule with a total of six protons. In the bulk phase, breaking the symmetry of the fully protonated state and creating singly and doubly charged anions induces proton transfer mechanisms. To demonstrate this, we used molecular dynamics (MD) simulations employing a variable topology approach based on the reasonably reliable semiempirical density functional tight binding (DFTB) evaluation of the atomic forces. We show that, by choosing common and economical starting compounds, we can devise a viable prototype for a highly conductive medium where charge transfer is achieved by proton motion.
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Ab Initio Molecular Dynamics Study of Phospho-Amino Acid-Based Ionic Liquids: Formation of Zwitterionic Anions in the Presence of Acidic Side Chains
Anno: 2020
Rivista: JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL
Autori/autrici: Adenusi, H.; Le Donne, A.; Porcelli, F.; Bodo, E.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330843
Citazioni:
Ab Initio Molecular Dynamics Study of Phospho-Amino Acid-Based Ionic Liquids: Formation of Zwitterionic Anions in the Presence of Acidic Side Chains / Adenusi, H.; Le Donne, A.; Porcelli, F.; Bodo, E.. - In: JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL. - ISSN 1520-6106. - 124:10(2020), pp. 1955-1964. [10.1021/acs.jpcb.9b09703]
Abstract:
We present a computational analysis of the complex proton-transfer processes in two protic ionic liquids based on phosphorylated amino acid anions. The structure and the short time dynamics have been analyzed via ab initio and semi-empirical molecular dynamics. Given the presence of mobile protons o...n the side chain, such ionic liquids may represent a viable prototype of highly conductive ionic mediums. The results of our simulations are not entirely satisfactory in this respect. Our results indicate that conduction in these liquids may be limited due to a quick quenching of the proton-transfer processes. In particular, we have found that, while proton migration does occur on very short timescales, the amino groups act as proton scavengers preventing an efficient proton migration. Despite their limits as conductive mediums, we show that these ionic liquids possess an unconventional microscopic structure, where the anionic component is made by amino acid anions that the aforementioned proton transfer has transformed into zwitterionic isomers. This unusual chemical structure is relevant because of the recent use of amino acid-based ionic liquids, such as CO2 absorbent.
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CO2 Capture in Ionic Liquids Based on Amino Acid Anions With Protic Side Chains: a Computational Assessment of Kinetically Efficient Reaction Mechanisms
Anno: 2020
Rivista: CHEMISTRYOPEN
Autori/autrici: Onofri, S.; Adenusi, H.; Le Donne, A.; Bodo, E.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330845
Citazioni:
CO2 Capture in Ionic Liquids Based on Amino Acid Anions With Protic Side Chains: a Computational Assessment of Kinetically Efficient Reaction Mechanisms / Onofri, S.; Adenusi, H.; Le Donne, A.; Bodo, E.. - In: CHEMISTRYOPEN. - ISSN 2191-1363. - 9:11(2020), pp. 1153-1160. [10.1002/open.202000275]
Abstract:
Absorption and capture of CO2 directly from sources represents one of the major tools to reduce its emission in the troposphere. One of the possibilities is to incorporate CO2 inside a liquid exploiting its propensity to react with amino groups to yield carbamic acid or carbamates. A particular clas...s of ionic liquids, based on amino acids, appear to represent a possible efficient medium for CO2 capture because, at difference with current industrial setups, they have the appeal of a biocompatible and environmentally benign solution. We have investigated, by means of highly accurate computations, the feasibility of the reaction that incorporates CO2 in an amino acid anion with a protic side chain and ultimately transforms it into a carbamate derivative. Through an extensive exploration of the possible reaction mechanisms, we have found that different prototypes of amino acid anions present barrierless reaction mechanisms toward CO2 absorption.
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Structural Features of Cholinium Based Protic Ionic Liquids through Molecular Dynamics
Anno: 2019
Rivista: JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL
Autori/autrici: Le Donne, A.; Adenusi, H.; Porcelli, F.; Bodo, E.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330841
Citazioni:
Structural Features of Cholinium Based Protic Ionic Liquids through Molecular Dynamics / Le Donne, A.; Adenusi, H.; Porcelli, F.; Bodo, E.. - In: JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL. - ISSN 1520-6106. - 123:26(2019), pp. 5568-5576. [10.1021/acs.jpcb.9b03314]
Abstract:
An analysis of the complex proton transfer processes in certain protic ionic liquids, based on amino acid anions, has been carried out through ab initio molecular dynamics in the view of finding naturally conductive and pure mediums. The systems analyzed here might serve as chemical prototypes for p...ure and dry ionic liquids where mobile protons can act as fast charge carriers. We have exploited the natural tendency of these liquids to form a complex network of hydrogen bonds. The presence of such a network allows the naturally repulsive interaction between like charge ions to be weakened to the point that a proton migration process inside the anionic component of the fluid becomes possible. We have also seen that the extent of these proton migrations is sizable for carboxylic based amino acid anions, while it is very limited for sulfur containing ones.
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Hydrogen Bonding as a Clustering Agent in Protic Ionic Liquids: Like-Charge vs Opposite-Charge Dimer Formation
Anno: 2018
Rivista: ACS OMEGA
Autori/autrici: Le Donne, A.; Adenusi, H.; Porcelli, F.; Bodo, E.
Lingua: ENG
Classificazione IRIS: 1.1 Articolo in rivista
Scheda completa IRIS: https://iris.univpm.it/handle/11566/330832
Citazioni:
Hydrogen Bonding as a Clustering Agent in Protic Ionic Liquids: Like-Charge vs Opposite-Charge Dimer Formation / Le Donne, A.; Adenusi, H.; Porcelli, F.; Bodo, E.. - In: ACS OMEGA. - ISSN 2470-1343. - 3:9(2018), pp. 10589-10600. [10.1021/acsomega.8b01615]
Abstract:
The local structure of a series of homologous protic ionic liquids (PILs) is investigated using ab initio computations and ab initio-based molecular dynamics. The purpose of this work is to show that in PILs the network of hydrogen bonds may promote like-charge clustering between anionic species. We... correlate the theoretical evidence of this possibility with viscosity experimental data. The homologous series of liquids is obtained by coupling choline with amino acid anions and varying the side chain. We find that the frictional properties of the liquids are clearly connected to the ability of the side chain to establish additional hydrogen bonds (other than the trivial cation-anion interaction). We also show that the large variation of bulk properties along the series of compounds can be explained by assuming that one of the sources of friction in the bulk liquid is the like-charge interaction between anions.
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