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1
Lee, Moon Joo, Ji Hoon Kim, Hyung-Seok Lim, So Young Lee, Hyung Kyun Yu, Jong Hun Kim, Joo Sung Lee et al. "Correction: Highly lithium-ion conductive battery separators from thermally rearranged polybenzoxazole". Chemical Communications 51, n. 16 (2015): 3474. http://dx.doi.org/10.1039/c5cc90064f.
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Li, Wei-Jie, Shu-Lei Chou, Jia-Zhao Wang, Hua-Kun Liu e Shi-Xue Dou. "Correction: A new, cheap, and productive FeP anode material for sodium-ion batteries". Chemical Communications 51, n. 22 (2015): 4720. http://dx.doi.org/10.1039/c5cc90084k.
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Sato, Shunsuke, Brendon J. McNicholas e Robert H. Grubbs. "Correction: Aqueous electrocatalytic CO2 reduction using metal complexes dispersed in polymer ion gels". Chemical Communications 56, n. 34 (2020): 4736. http://dx.doi.org/10.1039/d0cc90165b.
4
Shin, Mingyeong, Sujin Seo, In-Hyeok Park, Eunji Lee, Yoichi Habata e Shim Sung Lee. "Correction: Metallosupramolecules of pillar[5]-bis-trithiacrown including a mercury(ii) iodide ion-triplet complex". Chemical Communications 56, n. 73 (2020): 10766. http://dx.doi.org/10.1039/d0cc90380a.
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Li, Shiwu, Meng Gao, Shuxia Wang, Rongrong Hu, Zujin Zhao, Anjun Qin e Ben Zhong Tang. "Correction: Light up detection of heparin based on aggregation-induced emission and synergistic counter ion displacement". Chemical Communications 53, n. 39 (2017): 5432. http://dx.doi.org/10.1039/c7cc90160g.
6
Dong, Lei, Yi Zang, Dan Zhou, Xiao-Peng He, Guo-Rong Chen, Tony D. James e Jia Li. "Correction: Glycosylation enhances the aqueous sensitivity and lowers the cytotoxicity of a naphthalimide zinc ion fluorescence probe". Chemical Communications 51, n. 60 (2015): 12138. http://dx.doi.org/10.1039/c5cc90313k.
Abstract (sommario):
Correction for ‘Glycosylation enhances the aqueous sensitivity and lowers the cytotoxicity of a naphthalimide zinc ion fluorescence probe’ by Lei Dong et al., Chem. Commun., 2015, DOI: 10.1039/c5cc04357c.
7
Zhu, Congcong, Yunfei Teng, Ganhua Xie, Pei Li, Yongchao Qian, Bo Niu, Pei Liu et al. "Correction: Bioinspired hydrogel-based nanofluidic ionic diodes: nano-confined network tuning and ion transport regulation". Chemical Communications 56, n. 73 (2020): 10767. http://dx.doi.org/10.1039/d0cc90381g.
Abstract (sommario):
Correction for ‘Bioinspired hydrogel-based nanofluidic ionic diodes: nano-confined network tuning and ion transport regulation’ by Congcong Zhu et al., Chem. Commun., 2020, 56, 8123–8126, DOI: 10.1039/D0CC01313G.
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Zou, Kangyu, Peng Cai, Xinglan Deng, Baowei Wang, Cheng Liu, Zheng Luo, Xiaoming Lou, Hongshuai Hou, Guoqiang Zou e Xiaobo Ji. "Correction: Highly stable zinc metal anode enabled by oxygen functional groups for advanced Zn-ion supercapacitors". Chemical Communications 57, n. 20 (2021): 2571–72. http://dx.doi.org/10.1039/d1cc90077c.
Abstract (sommario):
Correction for ‘Highly stable zinc metal anode enabled by oxygen functional groups for advanced Zn-ion supercapacitors’ by Kangyu Zou et al., Chem. Commun., 2021, 57, 528–531, DOI: 10.1039/D0CC07526D.
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Chen, Qingze, Runliang Zhu, Qiuzhi He, Shaohong Liu, Dingcai Wu, Haoyang Fu, Jing Du, Jianxi Zhu e Hongping He. "Correction: In situ synthesis of a silicon flake/nitrogen-doped graphene-like carbon composite from organoclay for high-performance lithium-ion battery anodes". Chemical Communications 55, n. 22 (2019): 3302. http://dx.doi.org/10.1039/c9cc90105a.
Abstract (sommario):
Correction for ‘In situ synthesis of a silicon flake/nitrogen-doped graphene-like carbon composite from organoclay for high-performance lithium-ion battery anodes’ by Qingze Chen et al., Chem. Commun., 2019, 55, 2644–2647.
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Beale, A. M., I. Lezcano-Gonzalez, W. A. Slawinski e D. S. Wragg. "Correction: Correlation between Cu ion migration behaviour and deNOx activity in Cu-SSZ-13 for the standard NH3-SCR reaction". Chemical Communications 55, n. 11 (2019): 1667. http://dx.doi.org/10.1039/c9cc90036e.
Abstract (sommario):
Correction for ‘Correlation between Cu ion migration behaviour and deNOx activity in Cu-SSZ-13 for the standard NH3-SCR reaction’ by A. M. Beale et al., Chem. Commun., 2016, 52, 6170–6173.
11
Zhang, Liao, Yanyu Qu, Jiangtao Huang, Xiang Feng, De Li e Yong Chen. "Correction: Memory-effect-induced electrochemical oscillation of an Al-doped Li4Ti5O12 composite in Li-ion batteries". Chemical Communications 55, n. 64 (2019): 9568. http://dx.doi.org/10.1039/c9cc90335f.
Abstract (sommario):
Correction for ‘Memory-effect-induced electrochemical oscillation of an Al-doped Li4Ti5O12 composite in Li-ion batteries’ by Liao Zhang et al., Chem. Commun., 2019, 55, 1279–1282.
12
Liu, Yijin. "(Invited) A Macro-to-Nano Zoom through the Hierarchy of a Lithium Ion Battery". ECS Meeting Abstracts MA2022-01, n. 38 (7 luglio 2022): 1650. http://dx.doi.org/10.1149/ma2022-01381650mtgabs.
Abstract (sommario):
Lithium-ion battery (LIB) is featured by structural and chemical complexities across a broad range of length scales and, ultimately, it is the hierarchy of the battery structure that determines its functionality. The study of the battery function, degradation, and failure mechanisms requires a thorough and systematic investigation from the structural, chemical, mechanical, and dynamic perspectives. X-ray-based characterization techniques are playing an important role in this research field. In this talk, I will review my group’s research activities over the past few years [1-10] by presenting a macro-to-nano zoom through the hierarchy of a standard battery cell [2] using a suite of state-of-the-art X-ray techniques. Damage [6-7], deformation, compositional [9-10] and chemical [1, 4-5] heterogeneity at different length scales are visualized and are associated to different degradation phenomena and mechanisms. Our results highlight the importance of the battery cathode material’s mechanical properties [7-8], which evolve upon battery cycling and could significantly impact both the immediate and the long-term cell behaviours. Statistical analysis, numerical modelling [4], and machine learning [3, 5-6] approaches are key components integrated in our research efforts and will be touched upon in this presentation. I hope this presentation will ignite enthusiasm and ideas for future collaborations. References: (1) J. Zhang et al., Nat. Commun. 11 (2020) 6342. (2) G. Zan et al., J. Mater. Chem. A (2021) DOI: 10.1039/D1TA02262H. (3) Z. Jiang et al., Nat. Commun. 11 (2020) 2310. (4) S. Li et al., Nat. Commun. 11 (2020) 4433. (5) G. Qian et al., ACS Energy Lett. 6 (2021) 687–693. (6) Y. Mao et al., Adv. Func. Mater. (2019) 1900247. (7) S. Xia et al., Nano Energy 53 (2018) 753-762. (8) C. Wei et al., Acc. Chem. Res. 51 (2018) 2484-2492. (9) J.-N. Zhang et al., Nat. Energy 4 (2019) 594–603. (10) F. Lin et al., Nat. Energy 1 (2016) 15004.
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Ting, Yin-Ying, e Piotr M. Kowalski. "(Best Student Presentation) Accurate First-Principle Study of High-Entropy Materials for Lithium-Ion Batteries". ECS Meeting Abstracts MA2023-01, n. 4 (28 agosto 2023): 851. http://dx.doi.org/10.1149/ma2023-014851mtgabs.
Abstract (sommario):
The availability of well performing and cost efficient energy storage devices is of utmost importance for a smooth transition to sustainable energy. Lithium-ion batteries (LIBs) have been successfully commercialized and widely used in various portable devices. Functional materials with higher voltages and greater capacity are needed to further boost the energy density of these batteries. Recently, high-entropy materials (HEMs), with their unique structural characteristics and tunable functional properties, are actively investigated by several research groups [1]. High-entropy alloys (HEAs) with superior mechanical properties were first reported about a decade ago. Afterwards, the concept was adapted to high-entropy ceramic (HECs), such as high-entropy oxides, which are promising materials for electrodes as well as electrolytes in LIBs [2-4]. These materials usually contain more than 5 metals in a single disordered phase [5]. HECs are constructed with different type of cations and anions. Their structural and electronic complexity represent a challenge to the computational methods. We discuss the refined Density Functional Theory (DFT)-based methods that are able to successfully describe the electronic structure of these materials. The correct assignment of oxidation states of transition metals is one of the challenges, and we will show importance of correct description of d orbitals for achieving this task. Besides, we will also discuss the cycling performance, as well as thermodynamic aspects of selected HECs [6,7]. Last but not least, we will briefly discuss how accurate atomistic simulations could accelerate design of high-performance materials for Li-ion batteries of the future. [1] Zhang, R.-Z. & Reece, M. J. Review of high entropy ceramics: design, synthesis, structure and properties. J. Mater. Chem. A 7, 22148–22162 (2019). [2] Lun, Z. et al. Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries. Nat. Mater. 20, 214–221 (2021). [3] Sarkar, A. et al. High entropy oxides for reversible energy storage. Nat Commun 9, 3400 (2018). [4] Jung, S.-K. et al. Unlocking the hidden chemical space in cubic-phase garnet solid electrolyte for efficient quasi-all-solid-state lithium batteries. Nat Commun 13, 7638 (2022). [5] Rost, C. M. et al. Entropy-stabilized oxides. Nat Commun 6, 8485 (2015). [6] Cui, Y. et al. High entropy fluorides as conversion cathodes with tailorable electrochemical performance. Journal of Energy Chemistry 72, 342–351 (2022). [7] Ting,Y. & Kowalski, P., Refined DFT+U method for computation of layered oxide cathode materials, Electrochimica Acta, in press.
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Birge, N., V. Geppert-Kleinrath, C. Danly, B. Haines, S. T. Ivancic, J. Jorgenson, J. Katz et al. "Instrument design for an inertial confinement fusion ion temperature imager". Review of Scientific Instruments 93, n. 11 (1 novembre 2022): 113510. http://dx.doi.org/10.1063/5.0101820.
Abstract (sommario):
A mix of contaminant mass is a known, performance-limiting factor for laser-driven inertial confinement fusion (ICF). It has also recently been shown that the contaminant mass is not necessarily in thermal equilibrium with the deuterium–tritium plasma [B. M. Haines et al., Nat. Commun. 11, 544 (2020)]. Contaminant mass temperature is one of the dominant uncertainties in contaminant mass estimates. The MixIT diagnostic is a new and potentially transformative diagnostic, capable of spatially resolving ion temperature. The approach combines principles of neutron time-of-flight and neutron imaging diagnostics. The information from the MixIT diagnostic can be used to optimize ICF target and laser drive designs as well as provide key constraints on ICF radiation-hydrodynamic simulations that are critical to contaminant mass estimates. This work details the design and optimization of the major components of the MixIT diagnostic: the neutron aperture, the neutron detector (scintillator), and the recording system.
15
Dewan, Himani, R. Uma e R. P. Sharma. "Nonlinear evolution of Kinetic Alfvén Wave and the associated turbulence spectra in laser produced plasmas and laboratory simulation of astrophysical phenomena". Plasma Physics and Controlled Fusion 63, n. 12 (16 novembre 2021): 125034. http://dx.doi.org/10.1088/1361-6587/ac35a4.
Abstract (sommario):
Abstract This investigation presents the nonlinear interplay between pump wave (Kinetic Alfvén Wave (KAW)) and low-frequency ion acoustic wave (IAW) in the magnetized plasma. The model is developed by taking into account the ponderomotive nonlinearity associated due to the pump KAW. The coupled dimensionless equations (pump and IAW) are solved by adopting numerical simulation technique. The deduced results give the localization and filamentary structures of KAW, which eventually become chaotic with the evolution of time. The fundamental physics governing the dynamics of these two waves is influenced by the plasma beta ( β ) parameter; thereby affecting the nature of nonlinearity, dispersive properties and magnetic field amplification. The saturated spectra are analogous to that observed for many astrophysical scenarios for low (Chatterjee et al 2017 Nat. Commun. 8 15970) and high beta (White et al 2019 Nat. Commun. 10 1758; Tzeferacos et al 2017 Phys. Plasmas 24 041404) plasma. This theoretical model outlining the nonlinear interaction can be imperative in understanding the dynamics of magnetic field amplification in various astrophysical scenarios.
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Yadav, Jaya, Sai Pranav Vanam, Baskar Senthilkumar, Penphitcha Amonpattaratkit e Prabeer Barpanda. "Manganese-Based Tunnel and Layered Oxide Cathodes for Secondary Alkali-Ion Batteries". ECS Meeting Abstracts MA2023-02, n. 4 (22 dicembre 2023): 723. http://dx.doi.org/10.1149/ma2023-024723mtgabs.
Abstract (sommario):
Designing new cathode materials remains crucial in developing (post) Li-ion batteries. Mn-based oxide cathodes have received wide attention due to their sustainable nature, low cost, elemental abundance, structural diversity/polymorphism, and rich oxidation states (2+ to 7+), offering tunable redox potential [1]. Here, we have investigated different oxide-based cathode insertion compounds for secondary metal-ion batteries. i) We have demonstrated tunnel-type sodium insertion material Na44MnO2(NMO) as an intercalation host for Li-ion and K-ion batteries. The solution combustion synthesized Na0.44MnO2 assuming an orthorhombic structure (space group Pbam), exhibited rod-like morphology. After electrochemical ion exchange from NMO, we obtained Na0.11K0.27MnO2 (NKMO) and Na0.18Li0.51MnO2 (NLMO) cathodes for K-ion batteries and Li-ion batteries, respectively [2]. These new compositions, NKMO and NLMO, showed excellent cycling stability with capacities of ∼74 and 141 mAh g–1 (first cycle, C/20 current rate). The underlying mechanistic features concerning charge storage and structural modifications in these cathode compositions were probed by combining ex-situ structural, spectroscopy, and electrochemical tools [3]. ii) Using composite formation, we have tried to improve the P2-type layered material. Here, the stable Na7(Li1/18Mn1/18Ni3/18Fe2/18χ1/18)O2–xNa2MoO4 biphasic composite was synthesized using Mo doping. Overall, the redox chemistry was investigated using various spectroscopy techniques to prove the net capacity resulted from both cationic and anionic redox reactions [4]. Keywords: energy storage; batteries; cathode; manganese oxides; intercalation; doping References: [1] N. O. Vitoriano et al., T. Rojo, Energy Environ. Sci. 2017, 10 (5), 1051−1074. [2] K. Sada, B. Senthilkumar, P. Barpanda, Chem. Commun. 2017, 53 (61), 8588−8591. [3] S.P. Vanam et al., P. Barpanda, Inorg. Chem. 2022, 61 (9), 3959−3969. [4] S.P. Vanam, P. Barpanda, Electrochim. Acta. 2022, 431, 141122.
17
Jun, KyuJung, Byungju Lee e Gerbrand Ceder. "Elucidating the Role of Anion Groups in Lithium-Ion Diffusion". ECS Meeting Abstracts MA2023-02, n. 4 (22 dicembre 2023): 529. http://dx.doi.org/10.1149/ma2023-024529mtgabs.
Abstract (sommario):
Since the 1960s, the paddlewheel effect has been proposed as a way to enhance lithium-ion diffusion in inorganic materials by using rotor-like anion groups to assist lithium-ion movement(1–5). However, so far the physical mechanism behind how anion-group dynamics affect lithium-ion diffusion has not been clearly understood. In this talk, we clearly define various types of rotational motions of anion-groups. Based on such definition, we detect and differentiate such distinct anion-group rotational motions throughout a total of 10’s of ns ab-initio molecular dynamics trajectories. By performing rigorous statistical analysis of various rotational events as well as lithium-ion diffusion events, we reveal how each type of anion rotational motions are related to lithium-ion diffusion. Our research has finally resolved the ongoing debate about the existence of the paddlewheel effect and provide a clear physical understanding of how anion-group rotations are related to fast ionic diffusion in inorganic materials. L. Karlsson, R. L. McGreevy, Mechanisms of ionic conduction in Li2SO4 and LiNaSO4: Paddle wheel or percolation? Solid State Ionics. 76, 301–308 (1995). A. Kvist, A. Lundén, Electrical Conductivity of Solid and Molten Lithium Sulfate. Zeitschrift Für Naturforschung. 20, 235–238 (1965). Z. Zhang, L. F. Nazar, Exploiting the paddle-wheel mechanism for the design of fast ion conductors. Nat Rev Mater, 1–17 (2022). J. G. Smith, D. J. Siegel, Low-temperature paddlewheel effect in glassy solid electrolytes. Nat Commun. 11, 1483 (2020). M. Jansen, Volume Effect or Paddle‐Wheel Mechanism—Fast Alkali‐Metal Ionic Conduction in Solids with Rotationally Disordered Complex Anions. Angewandte Chemie Int Ed Engl. 30, 1547–1558 (1991).
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Oh, Gwangeon, e Jang-Yeon Hwang. "Enhancing the Electrochemical Properties of the Layered-Type K0.4V2O5 Cathode Materials through Cationic Metal Substitution in K Sites". ECS Meeting Abstracts MA2023-01, n. 3 (28 agosto 2023): 783. http://dx.doi.org/10.1149/ma2023-013783mtgabs.
Abstract (sommario):
Layered-type K0.4V2O5 have been widely investigated as cathode materials for potassium-ion batteries (PIBs) due to their high specific capacity. [1,2] However, sluggish intercalation kinetics of K ions into their crystal structure generally result in drastic capacity fading and poor power capability. [3] Here, we present significantly enhanced K-ion storage performances of the layered-type K0.4V2O5 cathode enabled by substitution of cationic metal for K-site. Density functional theory calculations data indicates that cationic metal prefer to occupy the K-site than transition metal layer. During charge and discharge process, inactive cationic metal acts as a pillar, thereby suppressing the irreversible phase transition and structural deterioration. In addition, cationic metal creates vacancies at k site, improving K-ion diffusion kinetics. Compared to K0.4V2O5, the modified cathode demonstrated the better cycling stability and power capability. A insitu X-ray diffraction and X-ray absorption near edge structure was used to verify role of cationic metal in improving electrochemical performance of the K0.4V2O5 cathode. Deng, X. Niu, G. Ma, Z. Yang, L. Zeng, Y. Zhu, L. Guo. Layered Potassium Vanadate K0.5V2O5 as a Cathode Material for Nonaqueous Potassium Ion Batteries, Adv. Func. Mater. 28 (2018) 1800670. Yang, Z. Liu, L. Deng, L. Tan, X. Niu, M. M. S. Sanad, L. Zeng, Y. Zhu. A Non-Topotactic Redox Reaction enabled K2V3O8 as a High Voltage Cathode Material for Potassium-Ion Batteries, Chem. Commun. 55 (2019) 14988–14991. Q. Fu, A. Sarapulove, L. Zhu, G. Melinte, A. Missyul, E. Welter, X. Luo, M. Knapp, H. Ehrenberg, S. Dsoke. In Operando Study of Orthorhombic V2O5 as Positive Electrode Materials for K-Ion Batteries, J. Energy Chem. 62 (2021) 627–636.
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Wang, Y. H., L. Wei, J. Yuan, R. W. Wang, J. D. Lu e L. L. Ji. "Retraction notice to “Optical limiting performance of Ag nanoclusters synthesized by ion implantation” [Opt. Commun. 287 (2012) 237–240]". Optics Communications 309 (novembre 2013): 359. http://dx.doi.org/10.1016/j.optcom.2013.10.029.
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Zhang, Bin. "Erratum to “ZPC 1.0.1: A parton cascade for ultrarelativistic heavy ion collisions” [Comput. Phys. Commun. 109 (1998) 193–206]". Computer Physics Communications 111, n. 1-3 (giugno 1998): 276. http://dx.doi.org/10.1016/s0010-4655(98)00035-6.
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Zuo, Wenhua, Guiliang Xu e Khalil Amine. "The Air Stability of Sodium Layered Oxide Cathodes". ECS Meeting Abstracts MA2022-02, n. 7 (9 ottobre 2022): 2594. http://dx.doi.org/10.1149/ma2022-0272594mtgabs.
Abstract (sommario):
Sodium-ion batteries (NIBs) are listed as one of the ideal alternatives for lithium-ion batteries (LIBs), due to the abundant sodium resources, cost-effective electrode materials of NIBs, and same architecture of NIBs to LIBs. To enable the practical implementation of NIBs, advanced cathodes with higher energy/power densities, better safety and cycle life, as well as lower cost are required. Layered lithium transition metal oxides (LiTMO2) are one of the most successful cathode materials for commercial LIBs. Similarly, layered sodium transition metal oxides (NaxTMO2, also termed as sodium layered oxides) are of particular interest for commercial NIBs owing to their high specific capacity, a wide variety of redox-active elements, and the possibility for the manufacturers to employ established synthesis processes as their lithium counterparts. Sodium layered oxides are built up by ordered stacking of alternate alkali-metal (Na+) layers and transition metal layers (TmO2). The two-dimensional structure makes them the natural hosts for alkali-metal ions and other ions or small molecules, such as H2O. Therefore, when exposed to moist atmospheres, layered oxide materials tend to react with H2O which adsorbed on their surface and thus deteriorate their structure and electrochemical performances. Accordingly, the air-sensitive sodium layered oxides should be well protected from the moist atmospheres, rendering a higher manufacturing and preservation cost. Here, based on the reaction mechanisms, critical influencing factors, and modification methods of layered oxides in moisture, we try to reach a comprehensive understanding of the air-stability of sodium layered oxides. Moreover, future efforts to resolve the air-stability of sodium layered oxides from Argonne National Laboratory will be also presented. References 1. Han, M. H.; Gonzalo, E.; Singh, G.; Rojo, T. A comprehensive review of sodium layered oxides: powerful cathodes for Na-ion batteries. Energy Environ. Sci. 2015, 8, 81-102. 2. Zuo, W.; Qiu, J.; Liu, X.; Ren, F.; Liu, H.; He, H.; Luo, C.; Li, J.; Ortiz, G. F.; Duan, H.; Liu, J.; Wang, M. S.; Li, Y.; Fu, R.; Yang, Y. The stability of P2-layered sodium transition metal oxides in ambient atmospheres. Commun. 2020, 11, 3544. 3. Xu, G. L.; Liu, X.; Zhou, X.; Zhao, C.; Hwang, I.; Daali, A.; Yang, Z.; Ren, Y.; Sun, C. J.; Chen, Z.; Liu, Y.; Amine, K. Native lattice strain induced structural earthquake in sodium layered oxide cathodes. Commun. 2022, 13, 436. 4. Zuo, W.; Xiao, Z.; Zarrabeitia, M.; Xue, X.; Yang, Y.; Passerini, S. Guidelines for Air-Stable Lithium/Sodium Layered Oxide Cathodes. ACS Materials Letters 2022, 4, 1074-1086. 5. Fu, F.; Liu, X.; Fu, X.; Chen, H.; Huang, L.; Fan, J.; Le, J.; Wang, Q.; Yang, W.; Ren, Y.; Amine, K.; Sun, S. G.; Xu, G. L. Entropy and crystal-facet modulation of P2-type layered cathodes for long-lasting sodium-based batteries. Commun. 2022, 13, 2826.
22
Wessells, Colin D. "(Invited) Recent Progress Towards Giga-Scale Sodium-Ion Batteries". ECS Meeting Abstracts MA2023-01, n. 5 (28 agosto 2023): 897. http://dx.doi.org/10.1149/ma2023-015897mtgabs.
Abstract (sommario):
Ongoing lithium-ion minerals supply chain volatility has driven price increases and supply shortages, and motivates the development and commercialization of alternative cell chemistries not dependent on those minerals.1-2 Among these alternative chemistries, sodium-ion cells offer promise due to the abundance and low cost of both sodium salts and typical electrode active species such as iron and manganese.2-3 Among sodium-ion electrode systems, Prussian blue analogues offer unique performance advantages including high C-rate charge and discharge, long cycle life, and thermal stability.4-6 Natron Energy has commercialized a unique sodium-ion cell in which each of the anode and cathode active materials are Prussian blue analogues. Products based on these cells are capable of full discharge at up to 60C, full recharge at up to 20C, and operate for tens of thousands of cycles without risk of thermal runaway. However, their energy density is limited by relatively low electrode specific capacities and cell voltage. This presentation will introduce the key materials science concepts that make Prussian blues a commercially viable materials system, as well as those that limit product performance, manufacturability, and the resulting applicable markets. In addition, Natron’s recent progress towards mass manufacturing of cells based on these materials will be summarized. This presentation will conclude with an overview of the key open scientific questions that must be answered for cost effective, giga-factory scale manufacturing of sodium-ion cells to become a reality. References: “2H 2021 Battery Metals Outlook: The Long Road to Recovery,” BloombergNEF, December 16, 2021. “Technology Radar: Sodium-Ion Batteries,” BloombergNEF, October 27, 2022. “2021 roadmap for sodium-ion batteries,” Nuria Tabia-Ruiz et al, 2021 J. Phys. Energy 3 031503. “Assessment of the first commercial Prussian blue based sodium-ion battery,” He, Minglong, et al, J. Power Sources 548 (2022) 232036. “Nickel Hexacyanoferrate Nanoparticle Electrodes for Aqueous Sodium and Potassium Ion Batteries,” Wessells, C.D., et al, Nano Letters 11 (2011) 5421-5425. “Monovalent manganese based anodes and co-solvent electrolyte for stable low-cost high-rate sodium-ion batteries,” Firouzi, A., et al, Nat. Commun. 9 (2018) 861.
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Das, Dhrubajyoti, Nagmani, Ananya Kumar e Sreeraj Puravankara. "Redox Shuttle Additives for Sodium-Ion Batteries". ECS Meeting Abstracts MA2023-02, n. 6 (22 dicembre 2023): 934. http://dx.doi.org/10.1149/ma2023-026934mtgabs.
Abstract (sommario):
Redox shuttle additives are already known in the battery field to provide overcharge protection, mainly at high-voltage cathode electrodes. The electroactive species can get either oxidized at the cathode side or reduced at the anode side, preferentially during the battery cycling. The mechanism involves the generation of positively charged radicals during oxidation and the subsequent diffusion and reduction at the anode surface. This shuttling process continues between the electrodes through baseline electrolytes. Redox shuttle additives are extensively studied in Li-ion batteries (LIBs).1–3 Benzophenone (BP) is one of the redox shuttle additives used successfully in lithium-ion batteries.4 No report exists in the literature for BP additives in sodium-ion batteries (SIBs). This work investigates BP (an already known overcharge protecting additive) and substituted 4-methyl BP (4-methyl benzophenone) as an electrolyte additive in baseline electrolyte containing NaClO4 in EC/PC solvent on both electrodes. The aim is to investigate BP's SEI-forming properties in sodium-ion batteries. The initial half-cell test with a Hard Carbon anode without and with 0.5 wt% 4-methyl BP as the additive is shown in Fig.1. 4-Methyl BP additive shows a large increase in specific capacity from 337 mAh gm-1 to 438 mAh gm-1 at 0.1C rate in a 5 mV - 1.5 V voltage range. The oral presentation will focus on the effect of additive concentration on the battery performance of HC and polyanionic cathode NVP in half-cell and full-cell configurations in Na-ion batteries. References: C. Buhrmester, L. Moshurchak, R. L. Wang, and J. R. Dahn, J. Electrochem. Soc., 153, A288 (2006). L. M. Moshurchak et al., J. Electrochem. Soc., 156, A309 (2009). M. Tang and J. Newman, J. Electrochem. Soc., 158, A530–A536 (2011). Q. Wang, S. M. Zakeeruddin, I. Exnar, and M. Grätzel, Electrochem. commun., 10, 651–654 (2008). Figure 1
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Ryu, S., H. Zhou, T. R. Paudel, N. Campbell, J. Podkaminer, C. W. Bark, T. Hernandez et al. "Electronic reconstruction at the polar (111)-oriented oxide interface". APL Materials 10, n. 3 (1 marzo 2022): 031115. http://dx.doi.org/10.1063/5.0067445.
Abstract (sommario):
Atomically flat (111) interfaces between insulating perovskite oxides provide a landscape for new electronic phenomena. For example, the graphene-like coordination between interfacial metallic ion layer pairs can lead to topologically protected states [Xiao et al., Nat. Commun. 2, 596 (2011) and A. Rüegg and G. A. Fiete, Phys. Rev. B 84, 201103 (2011)]. The metallic ion/metal oxide bilayers that comprise the unit cell of the perovskite (111) heterostructures require the interface to be polar, generating an intrinsic polar discontinuity [Chakhalian et al., Nat. Mater. 11, 92 (2012)]. Here, we investigate epitaxial heterostructures of (111)-oriented LaAlO3/SrTiO3 (LAO/STO). We find that during heterostructure growth, the LAO overlayer eliminates the structural reconstruction of the STO (111) surface with an electronic reconstruction, which determines the properties of the resulting two-dimensional conducting gas. This is confirmed by transport measurements, direct determination of the structure and atomic charge from coherent Bragg rod analysis, and theoretical calculations of electronic and structural characteristics. Interfacial behaviors of the kind discussed here may lead to new growth control parameters useful for electronic devices.
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Dwibedi, Debasmita, e Prabeer Barpanda. "Sodium Metal Sulphate Alluaudite Class of High Voltage Battery Insertion Materials". MRS Advances 3, n. 22 (2018): 1209–14. http://dx.doi.org/10.1557/adv.2018.132.
Abstract (sommario):
ABSTRACTElectrochemical energy storage has recently seen an exponential demand in the large-scale (power) grid storage sector. Earth abundant sodium-ion batteries are competent to enable this goal with economic viability. In a recent report in sodium-ion battery research, alluaudite framework Na2Fe2(SO4)3 has been reported with the highest Fe3+/Fe2+ redox potential (ca. 3.8 V, P. Barpanda, G. Oyama, S. Nishimura, S. C. Chung, and A. Yamada., Nature Commun. 5: 4358, 2014) with energy density comparable to the state-of-the-art Li-ion batteries. Material discovery is as essential as optimization of the existing materials to yield better performance for efficient energy storage. In a goal to optimize the synthesis of the reported alluaudite, this work first time reports the aqueous based Pechini synthesis for sodium metal sulphate alluaudite. It is a two-step method, where complexing agent plays a crucial role in holding the metal ions reserving their oxidation states. In the 2nd step, this complexing agent leaves the product with porous morphology. Taking advantage of its porous as well as 3D conductive framework, the complex attains fast electron/ion transport and sodium intercalation. Moreover, the single-phase reaction mechanism during sodium intercalation is reflected in its cycling property. It performs as a desirable cathode with operating potential as high as 3.7 V. While pursuing the synthesis, we observed an excess amount of sodium sulphate in the precursor mixture is needed to reduce the amount of impurities. To optimize the composition of the alluaudite phase and to explore novel compounds, we have carefully surveyed the Na2SO4-FeSO4 binary system. This work explores the possible compositional and structural flexibility in the Pechini synthesized alluaudites. A comparative study between compositional and redox activity in these samples will further inspire improvement of the alluaudite-type sodium metal sulphates for advanced sodium-ion batteries.
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Teranishi, Toshiharu. "(Invited, Digital Presentation) Transformations of Ionic Nanocrystals Via Ion Exchange Reactions". ECS Meeting Abstracts MA2022-01, n. 13 (7 luglio 2022): 930. http://dx.doi.org/10.1149/ma2022-0113930mtgabs.
Abstract (sommario):
Elaborate chemical synthesis methods allow the production of various types of inorganic nanocrystals (NCs) with uniform shape and size distributions. Then, how can we synthesize NCs with thermodynamically metastable phases or very complex structures? The transformation of already-synthesized NCs via elemental substitutions, such as ion exchange reactions for ionic NCs [1,2] and galvanic replacement reactions for metal NCs [3], can overcome the difficulties facing conventional one-step syntheses. In particular, NC ion exchange reactions have been studied with numerous combinations of foreign ions and ionic NCs with various shapes. The functionality of the resulting ionic NCs, including semiconducting and plasmonic properties, can be easily tuned in a wide range, from the visible to near-infrared. Here we focus on the full and partial ion exchange reactions involving ionic NCs, highlighting important aspects such as the preservation of appearance and dimensions [4,5]. Finally, visible-to-near infrared light energy conversion systems using partially exchanged ionic NCs are provided [6,7]. [1] Saruyama, M.; Sato, R.; Teranishi, T. Acc. Chem. Res. 2021, 54, 765. [2]Saruyama, M.; Teranishi, T. et al., J. Am. Chem. Soc. 2011, 133, 17598. [3] Sato, R.; Teranishi, T. et al., to be submitted. [4] Wu, H.-L.; Teranishi, T. et al., Science 2016, 351, 1306. [5] Li, Z.; Saruyama, M.; Asaka, T.; Tatetsu, Y.; Teranishi, T. Science 2021, 373, 332. [6] Lian, Z.; Teranishi, T. et al., Nat. Commun. 2018, 9, 2314. [7] Lian, Z.; Teranishi, T. et al., J. Am. Chem. Soc. 2019, 141, 2446.
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Sandra, Amritha, Ulriika Mattinen e Rakel Lindstrom. "An Insight into the Lithium Plating – Operando Gas Evolution Study". ECS Meeting Abstracts MA2023-02, n. 65 (22 dicembre 2023): 3086. http://dx.doi.org/10.1149/ma2023-02653086mtgabs.
Abstract (sommario):
Lithium-ion batteries (LiBs) play a major role in the electrification of transportation systems as a step forward in achieving a sustainable carbon neutral society [1]. Fast-charging is regarded as one of the most necessary features for lithium-ion batteries in order to speed the widespread adoption of electric vehicles [2]. However, we have previously shown that charging LiBs at high C-rate cause the evolution of high amount of ethylene gas along with capacity fade [3]. It is well known that fast charging is also may result in lithium plating and allied parasitic reactions [4]. Since many of the side reactions in LiBs are associated with evolution of products in gaseous phase, operando mass spectrometric techniques can be used to better understand these unwanted reactions. We have developed an Online Electrochemical Mass Spectrometry (OEMS) set-up to study the gases formed on a Li-plated electrode, to provide the fundamental understanding of the reaction mechanism at the electrode/electrolyte interface. References [1]. Bibra, E. M. et al. Global EV Outlook 2021: Accelerating Ambitions Despite the Pandemic. (2021). [2]. Huang, W., Ye, Y., Chen, H. et al. Onboard early detection and mitigation of lithium plating in fast-charging batteries. Nat Commun 13, 7091 (2022). [3]. Mattinen, Ulriika, et al. "Gas evolution in commercial Li-ion battery cells measured by on-line mass spectrometry–Effects of C-rate and cell voltage." Journal of Power Sources 477 (2020): 228968. [4]. Mussa, Abdilbari Shifa, et al. "Fast-charging to a partial state of charge in lithium-ion batteries: A comparative ageing study." Journal of Energy Storage 13 (2017): 325-333.
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Roy, Santanu, Abhijeet Prasad, Rahul Tevatia e Ravi F. Saraf. "Corrigendum to “Heavy metal ion detection on a microspot electrode using an optical electrochemical probe” [Electrochem. Commun. 86 (2018) 94–98]". Electrochemistry Communications 112 (marzo 2020): 106677. http://dx.doi.org/10.1016/j.elecom.2020.106677.
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Calvo, Ernesto J. "Erratum to “Scanning electrochemical microscopy measurement of ferrous ion fluxes during localized corrosion of iron” [Electrochem. Commun. 8 (2006) 179–183]". Electrochemistry Communications 8, n. 5 (maggio 2006): 909. http://dx.doi.org/10.1016/j.elecom.2006.03.004.
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Lu, Jun. "(Battery Division Technology Award) Understanding Metals' Roles in Layered Structure Oxides for High-Energy Lithium-ion Batteries". ECS Meeting Abstracts MA2022-02, n. 3 (9 ottobre 2022): 207. http://dx.doi.org/10.1149/ma2022-023207mtgabs.
Abstract (sommario):
The ever-increasing requirements in the high-energy density of lithium-ion batteries (LIBs) and current bottlenecks in cobalt supply place restrictions on the development of the state-of-the-art cathode materials with fine-tuned chemical composition by substituting the cobalt with nickel and manganese. In the layered structure ternary systems (LiNi1-y-zMnyCozO2, NCM), three transition-metal ions play a distinctive role that determines the physicochemical properties. A comprehensive understanding of the basic contribution of each transition metal is critical for further complete replacing expensive cobalt.[1] Here, we demonstrate cobalt and manganese behaviors by comparing various layered oxides with different chemical compositions to reveal their corresponding contributions.[2] Our results affirmed that cobalt plays an undeniable role in fast degradation, and found that cobalt is more destructive than Ni at high voltages. Even the possible instability induced by manganese (III) Jahn-Teller distortion [3], Mn(IV) substitution in the lattice can effectively alleviate this destructive and enables a high potential functionality. By further regulating the chemical composition with a concentration gradient strategy, Co-enriched surface and Mn-enriched core design in Ni-rich particles determines a robust structure, which can effectively suppress the owing to the low stiffness of the surface and stable structure in the core region. With these fundamental discoveries, we provide a guide for developing the promising Co-free cathodes to meet the increasing demand for high-energy density LIBs. References [1] M. Li, J. Lu. Science, 2020, 367, 979-980. [2] T. Liu, L. Yu, J. Liu, J. Lu, X. Bi, A. Dai, M. Li, M. Li, Z. Hu, L. Ma, D. Luo, J. Zheng, T. Wu, Y. Ren, J. Wen, F. Pan, K. Amine. Nat. Energy, 2021, 6, 277-286. [3] T. Liu, A. Dai, J. Lu, Y. Yuan, Y. Xiao, L. Yu, M. Li, J. Gim, L. Ma, J. Liu, C. Zhan, L. Li, J. Zheng, Y. Ren, T. Wu, R. S.-Yassar, J. Wen, F. Pan, K. Amine. Nat. Commun., 2019, 10, 4721. [4] T. Liu, L. Yu, J. Lu, T. Zhou, X. Huang, Z. Cai, A. Dai, J. Gim, Y. Ren, X. Xiao, M. V. Holt, Y. S. Chu, I. Arslan, J. Wen, K. Amine. Nat. Commun., 2021, 12, 6024.
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Hosono, Eiji, Daisuke Asakura, Wenxiong Zhang, Hayato Yuzawa, Masaki Kobayashi, Naoka Nagamura, Shingo Tanaka et al. "Analysis of Electrode Materials for Li-Ion Batteries by Synchrotron Soft X-Ray Microspectroscopy". ECS Meeting Abstracts MA2023-02, n. 2 (22 dicembre 2023): 204. http://dx.doi.org/10.1149/ma2023-022204mtgabs.
Abstract (sommario):
The development of clean energy devices such as Li-ion batteries is attracting attention in order to realize a low-carbon society. In addition to development of materials for Li-ion batteries, advanced analytical methods are also being developed to obtain the guideline of new materials and improve battery performance. We have been working on electronic structure analysis of transition metals and oxygen using synchrotron soft X-ray absorption and emission spectroscopy including ex-situ measurements and operando measurements. [1-3] We have also reported on synchrotron radiation micro-photoemission spectroscopy of all-solid-state Li-ion batteries using an operando measurement system. [4,5] In this presentation, we report analysis of each facet of a single crystalline LiCoO2 particle by resonant photoemission microspectroscopy. Resonant photoemission spectroscopy is element-selective method for obtaining valence band spectra using excitation energies around the absorption edge of target elements. Co 2p-3d absorption (L 2,3 absorption edge) of LiCoO2 was used to study the Co 3d orbitals near the Fermi level in detail. [6] Next, we report on the absorption spectroscopy of LiCoO2 using scanning transmission X-ray microscopy (STXM). The spatial resolution of about 100 nm can be used to analyze the chemical state distribution for each particle or within each particle. [7] References Electrochem. Commun. 50 (2015) 93-96. Phys. Chem. Chem. Phys. 21 (2019) 26351–26357. Phys. Chem. Chem. Phys. 24 (2022) 19177-19183. J. Electron Spectrsc. Relat. Phenom., 233 (2019) 64-68. Sci. Rep., 9 (2019) 12452. CrystEngComm, 25 (2023)183-188. Sci. Rep., 13 (2023) 4639.
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Li, Zheng, Dorthe B. Ravnsbæk, Kai Xiang e Yet-Ming Chiang. "Corrigendum to “Na3Ti2(PO4)3 as a sodium-bearing anode for rechargeable aqueous sodium-ion batteries” [Electrochem. Commun. 44 (2014) 12–15]". Electrochemistry Communications 44 (luglio 2014): 78. http://dx.doi.org/10.1016/j.elecom.2014.05.004.
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An, Qingbo, Shiyu Gan, Jianan Xu, Yu Bao, Tongshun Wu, Huijun Kong, Lijie Zhong, Yingming Ma, Zhongqian Song e Li Niu. "Corrigendum to “A multichannel electrochemical all-solid-state wearable potentiometric sensor for real-time sweat ion monitoring” [Electrochem. Commun. 107 (2019) 106553]". Electrochemistry Communications 110 (gennaio 2020): 106595. http://dx.doi.org/10.1016/j.elecom.2019.106595.
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Ock, S. A., e G. J. Rho. "232 PARTHENOGENETIC DEVELOPMENT AND PLOIDY OF BOVINE OOCYTES FOLLOWING VARIOUS CHEMICAL ACTIVATION REGIMENS". Reproduction, Fertility and Development 20, n. 1 (2008): 195. http://dx.doi.org/10.1071/rdv20n1ab232.
Abstract (sommario):
Bovine oocytes treated using various combinations of ionomycin (Ion), cycloheximide (CHX), and cytochalasin B (CCB) were evaluated for developmental rates and ploidy status. Metaphase II oocytes were allocated 5 treatment groups, and the groups were treated as follows: Group 1: 5 µm Ion for 5 min; Group 2: Ion + 10 µg mL–1 CHX for 5 h; Group 3: Ion + 10 µg mL–1 CHX + 5 µg mL–1 CCB for 1 h + 10 µg mL–1 CHX for 4 h; Group 4: Ion + 10 µg mL–1 CHX + 5 µg mL–1 CCB for 3 h + 10 µg mL–1 CHX for 2 h; and Group 5: Ion + 10 µg mL–1 CHX + 5 µg mL–1 CCB for 5. Difference among groups was analyzed using one-way ANOVA by SPSS 10.0 (SPSS, Inc., Chicago, IL, USA). In Experiment 1, 430 oocytes in 4 replicates were compared for the extrusion rate of the second polar body (PB) at 8 h after Ion treatment among groups. Group 5 exhibited significantly (P < 0.05) lower rates of second PB extrusion than did Groups 1–4 (22% v. 53–67%). Experiment 2 compared the rates of cleavage at 48 h and development to the blastocyst stage at 216 h after Ion treatment among groups. A total of 536 oocytes were used in 5 replicates. Parthenotes in Group 1 showed lower rates of cleavage and blastocyst development than those in other groups (20% and 1% v. 53–67% and 6–31%). Among the groups, parthenotes in Group 5 showed significantly (P < 0.05) higher blastocyst development. In Experiment 3, at 8 h after Ion treatment, oocytes from Groups 2, 3, and 5 were divided into two subgroups based on the presence or absence of the second PB, and assessed for cleavage rates and ploidy in 239 2-cell-stage parthenotes in 4 replicates, as described earlier by King et al. (1979 Vet. Sci. Commun. 3, 51–56). The cleavage rates did not differ among activation treatments, or by the presence or absence of the second PB in any activation group. The haploid rate was significantly (P < 0.05) higher in Group 2 than in Groups 3 and 5 (38% v. 19% and 0%, respectively). The diploid rate was significantly (P < 0.05) higher in Group 5 than in Groups 2 and 3 (88% v. 69% and 45%, respectively). In Experiment 4, the diploid rate of Group 2 blastocyst-stage parthenotes was 100% (4/4), whereas the diploid rates of Groups 3 and 5 blastocyst-stage parthenotes were 50% (6/12) and 71% (17/24), respectively, but the rates did not differ among groups. These results indicate that oocyte activation by CHX/CCB for 5 h after Ion treatment could enhance parthenogenetic development in bovines with higher rates of diploidy by preventing the extrusion of the second PB.
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Saneifar, Hamidreza, e Jian Liu. "Optimization of Loading Content of Li4Ti5O12-Hard Carbon Composite Anode for the Fast Charging Li-Ion Battery". ECS Meeting Abstracts MA2022-01, n. 2 (7 luglio 2022): 226. http://dx.doi.org/10.1149/ma2022-012226mtgabs.
Abstract (sommario):
Fast charge of lithium-ion batteries (LIBs) needs anode and cathode materials operating at high current densities. Li4Ti5O12 (LTO) can enable fast lithium ion (Li+) transport due to its 3D crystal structure. Nonetheless, this material suffers from low specific capacity and high operating voltage. In contrast, Hard Carbon (H.C) with high specific capacity and low practical voltage is one of the promising anode materials for high-energy lithium-ion batteries. However, practical application of this material is compromised with its slow kinetic, and reduced cycling performance associated with irreversibly trapped ions in its structure [1]. In this report, effect of loading ratio of H.C and LTO composite anode on the electrochemical behavior of fast charging lithium ion battery is studied. Electrochemical characterization results show that a certain loading of H.C plays a critical role in improving the electrochemical performance of LTO-H.C composite electrodes. Specifically, superior cycling stability and specific capacity achieved for the composite electrode with 20 wt.% H.C. It is believed that composite electrodes with an optimized ratio can effectively contribute to Li-ion storage and form a robust protective solid electrolyte interface (SEI) on the electrode surface. The latter might minimize further electrolyte decomposition and continuous growth of the SEI layer upon cycling, then improves the cycling stability of the electrode. In addition, the cycling performance and rate capability of LiNiMnCoO2 (NMC) with different nickel (Ni) and manganese (Mn) contents were evaluated and compared. The results clearly suggest that higher Ni content can improve specific capacity (115 mAhg-1for NMC333 vs 149 mAhg-1 for NMC811 at 1C). However, cycling stability deteriorates with increasing the Ni content (77% capacity retention for NMC333 vs 45% for NMC811 after 300 cycles). It is postulated that electrodes with higher Ni content are susceptible to transition metal dissolution and side reactions at electrode-electrolyte interface, which could lead to performance degradation by impeding Li+ diffusion across the electrode, and irreversible consumption of Li+ [2]. Finally, the possibility of use of the optimized anode for fabricating full cell with the selected NMC cathode is investigated. References: [1] Weiss, M., Ruess, R., Kasnatscheew, J. et al. Fast Charging of Lithium‐Ion Batteries: A Review of Materials Aspects. Adv. Energy Mater 11,2101126 (2021). [2] Lin, R., Bak, SM., Shin, Y. et al. Hierarchical nickel valence gradient stabilizes high-nickel content layered cathode materials. Nat Commun 12, 2350 (2021).
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Muldoon, John. "(Battery Division Technology Award) An Odyssey Through the Uncharted Waters of Post Lithium-Ion Batteries". ECS Meeting Abstracts MA2023-02, n. 7 (22 dicembre 2023): 989. http://dx.doi.org/10.1149/ma2023-027989mtgabs.
Abstract (sommario):
Advanced energy storage technologies such as lithium-ion batteries have enabled the development of ubiquitous portable electronic devices and are critical to the development and widespread adoption of practical electric vehicles. While lithium-ion batteries represent the most advanced energy storage technology currently available commercially, the desire for significant improvement in energy density and cost has led to a strong interest in so-called “beyond lithium-ion” batteries such as sodium, lithium-air, lithium-sulfur, multivalent batteries and solid-state batteries. In this talk, I will guide you on an odyssey toward post li-ion batteries. In particular, we will travel through the peaks and valleys of multivalent1-4, lithium-sulfur5-8, and all-solid-state batteries9-12. References: Kim, H. S.; Arthur, T. S.; Allred, G. D.; Zajicek, J.; Newman, J. G.; Rodnyansky, A. E.; Oliver, A. G.; Boggess, W. C.; Muldoon, J. Nat. Commun. 2011, 2, 427. Muldoon, J.; B. Bucur, C.; G. Oliver, A.; Sugimoto, T.; Matsui, M.; Soo Kim, H.; D. Allred, G.; Zajicek, J.; Kotani, Y. Energy & Environmental Science 2012, 5 (3), 5941–5950. Muldoon, J.; Bucur, C. B.; Gregory, T. Chem. Rev. 2014, 114 (23), 11683–11720. Bonnick, P.; Muldoon, J. Advanced Functional Materials 2020, 30 (21), 1910510. Bucur, C. B.; Muldoon, J.; Lita, A. Energy Environ. Sci. 2016, 9 (3), 992–998. Bonnick, P.; Nagai, E.; Muldoon, J. Electrochem. Soc. 2018, 165 (1), A600. Bonnick, P.; Muldoon, J. Energy Environ. Sci. 2020, 13 (12), 4808–4833. Osada, N.; Bucur, C. B.; Aso, H.; Muldoon, J. Energy Environ. Sci. 2016, 9 (5), 1668–1673. Bonnick, P.; Niitani, K.; Nose, M.; Suto, K.; S. Arthur, T.; Muldoon, J. Mater. Chem. A 2019, 7 (42), 24173–24179. Bonnick, P.; Muldoon, J. Energy Environ. Sci. 2022, 15, 1840-1860. Muldoon, J.; Bucur, C. B.; Boaretto, N.; Gregory, T.; Di Noto, V. Polym. Rev. 2015, 55 (2), 208–246. Suto, K.; Bonnick, P.; Nagai, E.; Niitani, K.; Arthur, T. S.; Muldoon, J. Mater. Chem. A 2018, 6 (43), 21261–21265.
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Xu, Zheng-Long. "(Digital Presentation) Advanced Intercalation Electrode Materials for Calcium Rechargeable Batteries". ECS Meeting Abstracts MA2022-02, n. 1 (9 ottobre 2022): 11. http://dx.doi.org/10.1149/ma2022-02111mtgabs.
Abstract (sommario):
The growing demand for electric vehicles and stationary energy storage systems calls for developing next-generation batteries that combine high energy, high power and low cost. Among many post lithium-ion batteries, calcium rechargeable batteries utilizing divalent Ca2+ ion charge carriers are expected to offer clear benefits in affordability of batteries along with the potentially high energy density, due to the abundance of calcium in earth crust (46600 ppm versus 20 ppm for lithium) and the low redox potential of Ca/Ca2+ (-2.9 V vs. standard hydrogen electrode). Recent efforts on the development of negative electrodes, such as elemental calcium metal and natural graphite, has brought the rechargeable calcium chemistries a step closer to a practically feasible battery system. However, the lack of suitable cathode is the Achille’s heal of the calcium rechargeable battery technology.[1] The relatively large ionic radius and divalent nature of Ca ions make the intercalation kinetics generally sluggish in intercalation hosts. Moreover, a large Ca2+ intercalation is supposed to cause extended volume changes of the host, triggering a premature degradation of the electrode structure. In this talk, I would like to present our recent findings in graphite anode and polyanionic cathode materials as intercalation electrodes in high performance non-aqueous calcium rechargeable batteries. We demonstrated that a large amount of Ca ions can be reversibly (de)intercalation in graphite for Ca ion batteries by identifying a proper electrolyte to promote the solvated-ion co-intercalation reactions.[2] The solvated-Ca-ion co-intercalation chemistry is comprehensively investigated by combining first principle calculations and synchrotron in-situ X-ray diffraction. For cathodes, we find that the open-framework sodium vanadium fluorophosphate can function as a stable and fast-kinetic Ca2+ intercalation host with an extremely low capacity degradation rate of 0.02% per cycle over 500 cycles.[3] This value records the best stability reported for Ca ion battery cathodes so far. Through this talk, it is believed that the new findings in discovering novel materials or intercalation chemistries will be of great interest of the community working on multivalent ion batteries and other energy storage technologies. Reference: [1] C Chen, F Shi, ZL Xu, Advanced electrode materials for nonaqueous calcium rechargeable batteries, J. Mater. Chem. A, 2021, 9, 11908-11930 [2] Z.L. Xu, J. Park, J. Wang, H. Moon, G. Yoon, J. Lim, Y.J. Ko, S.P. Cho, S.Y. Lee and K. Kang, A new high-voltage calcium intercalation host for ultra-stable and high-power calcium rechargeable batteries, Nat. Commun. 2021, doi:10.1038/s41467-021-23703-x. [3] J. Park,† Z.L. Xu,† G. Yoon,† S.K. Park, J. Wang, H. Hyun, H. Park, J. Lim, Y.J. Ko and K. Kang, Stable and High power calcium ion batteries enabled by calcium intercalation in graphite, Adv. Mater. 2020, 32.4: 1904411.
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Kitsche, David, Aleksandr Kondrakov, Jürgen Janek e Torsten Brezesinski. "(Invited) ALD Coatings for Li-Ion Battery and All-Solid-State Battery Applications". ECS Meeting Abstracts MA2022-02, n. 31 (9 ottobre 2022): 1138. http://dx.doi.org/10.1149/ma2022-02311138mtgabs.
Abstract (sommario):
Lithium-ion batteries (LIBs) are essential for modern life, and their improvement is crucial for the more widespread adoption of electric vehicles.[1] Layered lithium transition metal oxides, such as LiNixCoyMnzO2 (often referred to as NCM or NMC), are among the most widely used cathode active materials (CAMs) for automotive applications, owing to their technological maturity and high energy density. However, they typically require a surface coating for stabilizing interfaces, both in liquid-electrolyte based LIBs and in solid-state battery (SSB) environments. For the preparation of protective CAM coatings, atomic layer deposition (ALD) stands out with its ability to produce conformal films on complex substrates. This presentation encompasses several examples of successful improvements in cycling performance of Ni-rich NCM CAMs in LIBs and SSBs by ALD of binary oxides. The low-temperature deposition of AlxOy onto ready-to-use cathode sheets will be discussed.[2] ALD or ALD-related surface protection enables increased stability by suppressing detrimental surface corrosion and metal leaching (side reactions) in LIBs.[2,3] Moreover, we report about the application of ALD coatings to Ni-rich NCM CAMs in SSBs with lithium thiophosphate solid electrolytes. Specifically, the effect that both HfO2 and ZrO2 have on the cell cyclability will be shown, with emphasis placed on the role of post annealing.[4] [1] Goodenough et al. J. Am. Chem. Soc. 2013, 135, 1167. [2] Neudeck et al. Sci. Rep. 2019, 9, 5328. [3] Neudeck et al. Chem. Commun. 2019, 55, 2174. [4] Kitsche et al. ACS Appl. Energy Mater. 2021, 4, 7338.
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Mendoza, S. A., J. A. Schneider, A. Lopez-Rivas, J. W. Sinnett-Smith e E. Rozengurt. "Early events elicited by bombesin and structurally related peptides in quiescent Swiss 3T3 cells. II. Changes in Na+ and Ca2+ fluxes, Na+/K+ pump activity, and intracellular pH." Journal of Cell Biology 102, n. 6 (1 giugno 1986): 2223–33. http://dx.doi.org/10.1083/jcb.102.6.2223.
Abstract (sommario):
The amphibian tetradecapeptide, bombesin, and structurally related peptides caused a marked increase in ouabain-sensitive 86Rb+ uptake (a measure of Na+/K+ pump activity) in quiescent Swiss 3T3 cells. This effect occurred within seconds after the addition of the peptide and appeared to be mediated by an increase in Na+ entry into the cells. The effect of bombesin on Na+ entry and Na+/K+ pump activity was concentration dependent with half-maximal stimulation occurring at 0.3-0.4 nM. The structurally related peptides litorin, gastrin-releasing peptide, and neuromedin B also stimulated ouabain-sensitive 86Rb+ uptake; the relative potencies of these peptides in stimulating the Na+/K+ pump were comparable to their potencies in increasing DNA synthesis (Zachary, I., and E. Rozengurt, 1985, Proc. Natl. Acad. Sci. USA., 82:7616-7620). Bombesin increased Na+ influx, at least in part, through an Na+/H+ antiport. The peptide augmented intracellular pH and this effect was abolished in the absence of extracellular Na+. In addition to monovalent ion transport, bombesin and the structurally related peptides rapidly increased the efflux of 45Ca2+ from quiescent Swiss 3T3 cells. This Ca2+ came from an intracellular pool and the efflux was associated with a 50% decrease in total intracellular Ca2+. The peptides also caused a rapid increase in cytosolic free calcium concentration. Prolonged pretreatment of Swiss 3T3 cells with phorbol dibutyrate, which causes a loss of protein kinase C activity (Rodriguez-Pena, A., and E. Rozengurt, 1984, Biochem. Biophys. Res. Commun., 120:1053-1059), greatly decreased the stimulation of 86Rb+ uptake and Na+ entry by bombesin implicating this phosphotransferase system in the mediation of part of these responses to bombesin. Since some activation of monovalent ion transport by bombesin was seen in phorbol dibutyrate-pretreated cells, it is likely that the peptide also stimulates monovalent ion transport by a second mechanism.
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Nogueira, M., G. Garcia, C. Mejuto e M. Freire. "Regulation of the pentose phosphate cycle Cofactor that controls the inhibition of glucose-6-phosphate dehydrogenase by NADPH in rat liver". Biochemical Journal 239, n. 3 (1 novembre 1986): 553–58. http://dx.doi.org/10.1042/bj2390553.
Abstract (sommario):
A cofactor of Mr 10(4), characterized as a polypeptide, was found to co-operate with GSSG to prevent the inhibition of glucose-6-phosphate dehydrogenase by NADPH, in order to ensure the operation of the oxidative phase of the pentose phosphate pathway, in rat liver [Eggleston & Krebs (1974) Biochem. J. 138, 425-435; Rodriguez-Segade, Carrion & Freire (1979) Biochem. Biophys. Res. Commun. 89, 148-154]. This cofactor has now been partially purified by ion-exchange chromatography and molecular gel filtration, and characterized as a protein of Mr 10(5). The lighter cofactor reported previously was apparently the result of proteolytic activity generated during the tissue homogenization. The heavier cofactor was unstable, and its amount increased in livers of rats fed on carbohydrate-rich diet. Since the purified cofactor contained no glutathione reductase activity, the involvement of this enzyme in the deinhibitory mechanism of glucose-6-phosphate dehydrogenase by NADPH should be ruled out.
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Castillo, C. J., P. Colburn e V. Buonassisi. "Characterization and N-terminal sequence of a heparan sulphate proteoglycan synthesized by endothelial cells in culture". Biochemical Journal 247, n. 3 (1 novembre 1987): 687–93. http://dx.doi.org/10.1042/bj2470687.
Abstract (sommario):
We have isolated from the conditioned medium of an established endothelial cell line a heparan sulphate proteoglycan whose involvement in the inhibition of the extrinsic coagulation pathway was reported in previous studies [Colburn & Buonassisi (1982) Biochem. Biophys. Res. Commun. 104, 220-227]. The proteoglycan was purified by gel filtration and ion-exchange chromatography, and appears to be free of contaminating proteins as determined by polyacrylamide-gel electrophoresis of the radioiodinated protein core before and after removal of the glycosaminoglycan chains by treatment with heparitinase. By this procedure the Mr of the protein core was estimated to be 22000. The N-terminal end was sequenced up to amino acid 25. The 21st residue is likely to be glycosylated. Analysis of the purified proteoglycan by gel-filtration chromatography yielded Kd values of 0.2 for the whole molecule and 0.35 for the glycosaminoglycan chains. The structure that emerges from these data is that of a heparan sulphate proteoglycan characterized by a relatively small protein core and few glycosaminoglycan chains.
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Loidl-Stahlhofen, A., K. Hannemann, R. Felde e G. Spiteller. "Epoxidation of plasmalogens: source for long-chain α-hydroxyaldehydes in subcellular fractions of bovine liver". Biochemical Journal 309, n. 3 (1 agosto 1995): 807–12. http://dx.doi.org/10.1042/bj3090807.
Abstract (sommario):
1. Masked long-chain alpha-hydroxyaldehydes were trapped in all subcellular fractions of bovine liver by application of pentafluorbenzyloxime derivatization [van Kuijk, Thomas, Stephens and Dratz (1986) Biochem. Biophys. Res. Commun. 139, 144-149] and quantified via GLC/MS using characteristic ion traces. 2. The chain-length profile of long-chain 2-hydroxyalkanales clearly indicates their relationship to plasmalogens as precursor molecules. 3. The previously postulated existence of alpha-acyloxyplasmalogens as precursor molecules of masked long-chain alpha-hydroxyaldehydes in bovine tissue lipids [Lutz and Spiteller (1991) Liebigs Ann. Chem. 1991, 563-567] was excluded. 4. The constant oxidation rate of plasmalogens in all subcellular fractions provides conclusive evidence for a non-enzymic plasmalogen epoxidation process (probably via hydroperoxy radicals). 5. The high reactivity of alpha-hydroxyaldehydes sheds some doubt on the postulation that plasmalogens protect mammalian cells against oxidative stress as postulated previously [Morand, Zoeller and Raetz (1988) J. Biol. Chem. 263, 11590-11596; Morand, Zoeller and Raetz (1988) J. Biol. Chem. 263, 11597-11606].
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Cattermull, John, Shobhan Dhir, Ben Jagger, Andrew Goodwin e Mauro Pasta. "Diffusion Kinetics in Multi-Phase K-Ion Cathodes". ECS Meeting Abstracts MA2023-02, n. 4 (22 dicembre 2023): 548. http://dx.doi.org/10.1149/ma2023-024548mtgabs.
Abstract (sommario):
Prussian blue analogues (PBAs) are a framework material that are of great interest for use as cathode materials in Na- and K-ion batteries. Na-ion PBA batteries have been commercialized for use in stationary storage and are now in development for use in electric vehicles. The high operating potential of K-ion PBAs and their compatibility with pre-existing graphite anodes offer the exciting prospect of use in electric vehicles where high specific energy density is necessary [1]. The leading cathode material is the Manganese/Iron PBA – K x Mn[Fe(CN)6] y (0<x<2, 0.67<y<1.00). Attempts to maximise the specific capacity of PBA cathodes have been made by eliminating [Fe(CN)6] vacancies (y=1) which incorporates a full x = 2 formula units of K+ ions in the structure through electronic balancing [2]. Whilst making these low-vacancy materials has been made possible by altering the synthesis, optimising the electrochemical performance has proved more challenging [3]. Accessing the full capacity with high retention on cycling is one problem, and achieving the same excellent rate capability of the previously studied high-vacancy PBAs is also non-trivial [3,4] . High-vacancy PBAs have an apparent simple cubic structure, and cycle electrochemically in a solid-solution [4]. Conversely, the low-vacancy PBAs with high K-ion content have coherent structural distortions and undergo phase transitions on cycling [3,5]. The phase transitions are believed to be responsible for poor capacity retention and rate capability [2]. There is also the theory that vacancies provide additional diffusion pathways for K+ ions [Fig. 1] [2]. For the development of this material as a cathode for K-ion batteries to be successful, it is vital that the diffusion kinetics and structural changes on electrochemical cycling are well-understood from a fundamental perspective. For the first time we report diffusion coefficients by using Potentiostatic Intermittent Titration across multiple states of charge of a PBA cathode [6]. Linking the ionic diffusion in the material with the structural phase(s) present from operando X-ray diffraction gives us a mechanistic insight into the cathode’s charge/discharge behaviour. This informs materials design for tuning the structure of the pristine material to optimise its electrochemical performance in a K-ion battery. References: [1] Hurlbutt, K.; Wheeler, S.; Capone, I.; Pasta, M. Prussian Blue Analogs as Battery Materials. Joule 2018, 2 (10), 1950–1960. [2] Cattermull, J.; Pasta, M.; Goodwin, A. L. Structural Complexity in Prussian Blue Analogues. Mater. Horiz. 2021, 8 (12), 3178–3186. [3] Bie, X.; Kubota, K.; Hosaka, T.; Chihara, K.; Komaba, S. A Novel K-Ion Battery: Hexacyanoferrate(II)/Graphite Cell. J. Mater. Chem. A 2017, 5 (9), 4325–4330. [4] Wessells, C. D.; Huggins, R. A.; Cui, Y. Copper Hexacyanoferrate Battery Electrodes with Long Cycle Life and High Power. Nat. Commun. 2011, 2 (1), 2–6. [5] Cattermull, J.; Sada, K.; Hurlbutt, K.; Cassidy, S. J.; Pasta, M.; Goodwin, A. L. Uncovering the Interplay of Competing Distortions in the Prussian Blue Analogue K2Cu[Fe(CN)6]. Chem. Mater. 2022, 34 (11), 5000–5008. [6] Cattermull, J.; Dhir S.; Jagger B.; Goodwin, A. L.; Pasta, M. Manuscript in preparation. Figure 1
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Zhang, Longsheng, Yunpeng Huang, Yue-E. Miao, Wei Fan e Tianxi Liu. "Corrigendum to “Hierarchical composites of NiCo2S4 nanorods grown on carbon nanofibers as anodes for high-performance lithium ion batteries”[Compos. Commun. 21 (2020) 100395]". Composites Communications 22 (dicembre 2020): 100525. http://dx.doi.org/10.1016/j.coco.2020.100525.
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Dayani, Shahabeddin, Henning Markötter, Anita Schmidt e Giovanni Bruno. "Towards Safer Batteries- 4D Imaging of Abuse Mechanisms in Lithium-Ion Batteries Using Synchrotron X-Ray Computed Tomography". ECS Meeting Abstracts MA2023-02, n. 3 (22 dicembre 2023): 493. http://dx.doi.org/10.1149/ma2023-023493mtgabs.
Abstract (sommario):
Higher energy density materials are being pushed by the research community to make lithium-ion batteries a better competitor to chemical fossil fuels for transport applications. This increases potential risk of lithium-ion batteries and therefore safety investigations are highly important for application purposes. Operando Computer Tomography provides a non-destructive investigation method of different abuse mechanisms. Application of X-ray computed tomography (XCT) for studying lithium-ion batteries has gained interest among the research community especially in the past decade [1]. This technique is widely used for ex-situ samples to measure porosity and tortuosity [2], particle size and volume distribution [3] in the graphite anode as well as different cathode materials such as LiCoOx and NiMnCoOx. [4]. In situ measurements of commercial batteries are also often carried out to detect defects induced in a cell by a safety abuse test or manufacturing process [5]. Operando CT of large cells (for example 18650 form factor) is conducted at synchrotron facilities with high flux of high energy photons, however at a cost of details due to the large field of view [6]. Thanks to their high brilliance, synchrotron beam facilitates us to do a full Computed Tomography in a short time. This enables us to measure batteries while being cycled with a reasonable time resolution to record morphological changes. In this presentation we illustrate how one can utilize this ability to investigate abuse mechanisms on an actual commercially available lithium-ion battery from cell level to electrode level. In this work, lab-based and synchrotron X-ray computed tomography is applied to commercial lithium-ion batteries. It is shown how to find most suitable imaging settings to study available lithium-ion batteries on different size scales, from cell level to particle level. We also demonstrate how to optimize contrast as well as both temporal and spatial resolutions to study in-situ and operando processes in a commercial battery using attenuation and phase contrast SXCT. Manufacturing defects and inconsistencies on cell level as well as the electrode and microstructure on material level are shown in our study. Using the presented methodic, some abuse conditions are induced and imaged in operando on a commercially available li-ion battery. In this work, deep discharge mechanism is visualized and quantified in detail for the first time in 4 dimensions. This oral presentation is aimed to present SXCT and lab XCT imaging as an important tool for studying state of safety of lithium-ion batteries from cell level down to particle level. It is shown how to find most suitable imaging settings to study available lithium-ion batteries on different size scales. We also demonstrate how to optimize contrast as well as both temporal and spatial resolutions to study in-situ and operando processes in a commercial battery using attenuation and phase contrast SXCT. Manufacturing defects and inconsistencies on cell level as well as the electrode and microstructure on material level are shown in our study. Moreover, some abuse conditions are imaged in operando in a commercially available li-ion battery. Le Houx, J. and D. Kramer, X-ray tomography for lithium ion battery electrode characterisation — A review. Energy Reports, 2021. 7: p. 9-14. Eastwood, D.S., et al., The application of phase contrast X-ray techniques for imaging Li-ion battery electrodes. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 2014. 324: p. 118-123. Finegan, D.P., et al., Investigating lithium-ion battery materials during overcharge-induced thermal runaway: an operando and multi-scale X-ray CT study. Phys Chem Chem Phys, 2016. 18(45): p. 30912-30919. Ebner, M., et al., Tortuosity Anisotropy in Lithium-Ion Battery Electrodes. Advanced Energy Materials, 2014. 4(5). Patel, D., et al., Thermal Runaway of a Li-Ion Battery Studied by Combined ARC and Multi-Length Scale X-ray CT. Journal of The Electrochemical Society, 2020. 167(9). Finegan, D.P., et al., In-operando high-speed tomography of lithium-ion batteries during thermal runaway. Nat Commun, 2015. 6: p. 6924.
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Barman, Pubali, Pawan Kumar Kumar Jha, Sai Gautam Gopalakrishnan, Pieremanuele Canepa e Prabeer Barpanda. "Probing the Mo-Redox in Alluaudite Battery Materials". ECS Meeting Abstracts MA2023-02, n. 4 (22 dicembre 2023): 795. http://dx.doi.org/10.1149/ma2023-024795mtgabs.
Abstract (sommario):
Alluaudites are essentially naturally occurring mixed metal (Mn and Fe) phosphate-based minerals [1] consisting of an open framework structure to support fast alkali migration. The general formula for alluaudite can be expressed by A(1)A(2)M(1)M(2)2(XO4)3 where A and M sites are alkali ion and transition metals respectively and X can be S, P, As, Mo, W, V and so on [2]. The presence of polyanionic moieties (XO4) assures structural stability and high-voltage operation arising from the inductive effect [3]. Till date, a variety of phosphate and sulfate-based alluaudites have been reported as cathodes for Li-ion and Na-ion batteries [4,5]. In 2017, the first molybdate-based alluaudite material, Na2.67Mn1.67(MoO4)3, was reported as a 3.45 V Mn-based cathode [6]. Inspired by this work, we have explored other 3d (Co, Ni) based molybdate alluaudite homologues as potential compounds with desirable electrochemical and electrocatalytic activities. Solution combustion synthesis was employed to prepare phase pure Na36Co1.32(MoO4)3 by restricting the annealing duration to one minute as compared to the reported solid-state route warranting prolonged (100 h) annealing. It was found to act as a high-voltage cathode (4 V vs Na/Na+ and 4.1 V vs Li/Li+) involving Co3+/Co2+ redox center [7] while cycling between 3.0 V to 4.3 V. The above-mentioned alluaudite consists of Mo species, which can be redox-active at lower voltages. When cycled in a low-voltage window (0.01 V to 3.0 V), this material was found to act as an anode for both Li-ion and Na-ion batteries. High capacity (ca 400-500 mAh/g) was obtained with a central potential ~0.6 V involving conversion and (de)insertion reaction mechanism. The Ni-analogue, Na4Ni0.8(MoO4)2 alluaudite, was studied as an anode material in both Li-ion and Na-ion batteries involving conversion and (de)intercalation redox mechanisms like the Co- analogue. The underlying redox mechanism will be described for both cases involving post-mortem diffraction, electron microscopy, and spectroscopic tools as well as with the help of the density functional theory (DFT) approach. Finally, alluaudite Na4Cu(MoO4)3 was prepared by soft chemistry route, which was found to work as an anode material in the voltage window of 0.01 V to 3.0 V. The phase transformation and underlying redox mechanism will be elucidated. References: [1] D. J. Fisher, Am. Mineral. 40 (1955) 1100-1109. [2] D. Dwibedi, P. Barpanda, A. Yamada, Small Methods 4 (2020) 2000051. [3] P. Barpanda, L. Lander, S. Nishimura, A. Yamada, Adv. Energy Mater. 8 (2018) 1703055. [4] P. Barpanda, G. Oyama, S. Nishimura, S.-C. Chung, A. Yamada, Nat. Commun. 5 (2014) 4358. [5] D. Dwibedi, R. Araujo, S. Chakraborty et al, R. Ahuja, P. Barpanda, J. Mater. Chem. A 3 (2015) 18564-18571. [6] J. Gao, P. Zhao, K. Feng, Chem. Mater. 29 (2017) 940-944. [7] P. Barman, P.K. Jha, A. Chaupatnaik et al, P. Barpanda, Mater. Today Chem. 27 (2023) 101316.
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Pham, Ngan K., Tuyen T. T. Truong, Kha Minh Le, Tuyen Thi Kim Huynh, Man V. Tran e Phung Le. "Nonflammable Sulfone-Based Electrolytes for Achieving High-Voltage Li-Ion Batteries Using LiNi0.5Mn1.5O4 Cathode Material". ECS Meeting Abstracts MA2022-01, n. 2 (7 luglio 2022): 291. http://dx.doi.org/10.1149/ma2022-012291mtgabs.
Abstract (sommario):
High voltage Li-ion batteries have been expected a forward technology designed for vehicles, marines and other high power and energy density applications 1–3. Among high voltage cathodes, LiNi0.5Mn1.5O4 is considered a promising cathode to reduce the battery cost as well as environmental hazard issues4,5. However, a high operation potential and Mn dissolution brings the most critical challenges for achieving the long cycle-life of Li-ion cell6,7. In this study, we report a rational design of nonflammable electrolyte based on LiBF4 and sulfolane (TMS) mixed with a dimethyl carbonate (DMC) as co-solvent to enhance conductivity. Among different molar ratios, the electrolyte LiBF4: TMS: DMC =1:2:1 in mol. exhibited the highest electrochemical stability (~ 6.1 V vs. Li+/Li) and ionic conductivity up to 1.57 mS.cm-1 at 30 oC. Cycling performance of LNMO/Li half-cell and LNMO/graphite full-cell cycled were carried out using the optimized electrolyte. While half-cells LNMO//Li display a high initial capacity of 118 mAh.g-1 and remain 56.48 % of initial value after 100 cycles, a full cell LNMO//Graphite with an areal loading of 1.0 mAh.cm-2 and low N/P ratio (~1.2) exhibited a better cycling stability than the one using commercial electrolyte 1M LiPF6/EC-DMC, 1:1 in vol (with initial capacity of 87 mAh.g-1 and capacity retention of 18% after 100 cycles8). References Goodenough JB, Kim Y. Challenges for Rechargeable Li Batteries. Chem Mater. 2010;22(3):587-603. Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D. Challenges in the development of advanced Li-ion batteries: a review. Energy Environ Sci. 2011;4(9):3243. Amine K, Kanno R, Tzeng Y. Rechargeable lithium batteries and beyond: Progress, challenges, and future directions. MRS Bull. 2014;39(5):395-401. Kim J-H, Myung S-T, Sun Y-K. Molten salt synthesis of LiNi0.5Mn1.5O4 spinel for 5 V class cathode material of Li-ion secondary battery. Electrochim Acta. 2004;49(2):219-227. Patoux S, Daniel L, Bourbon C. High voltage spinel oxides for Li-ion batteries: From the material research to the application. J Power Sources. 2009;189(1):344-352. Jang DH, Shin YJ, Oh SM. Dissolution of Spinel Oxides and Capacity Losses in 4 V Li / LixMn2O4 Cells. J Electrochem Soc. 1996;143(7):2204-2211. Du Pasquier A, Blyr A, Courjal P. Mechanism for Limited 55°C Storage Performance of Li1.05Mn1.95 O 4 Electrodes. J Electrochem Soc. 1999;146(2):428-436. Wang J, Yamada Y, Sodeyama K, Chiang CH, Tateyama Y, Yamada A. Superconcentrated electrolytes for a high-voltage lithium-ion battery. Nat Commun. 2016;7(1):12032. Acknowledgement This work is supported by Ho Chi Minh city - Department of Science and Technology (DOST) under grant number 54/2020/HĐ-QPTKHCN.
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Telmasre, Tushar Khemraj, Taejin Jang, Neha Goswami, Anthony Concepcion e Venkat R. Subramanian. "Simulation Strategies for Measuring Impedance Response of Lithium-Ion Batteries". ECS Meeting Abstracts MA2022-02, n. 2 (9 ottobre 2022): 115. http://dx.doi.org/10.1149/ma2022-022115mtgabs.
Abstract (sommario):
The battery as an electrochemical system can be considered a Blackbox with no way of observing processes occurring within it in a nondestructive manner1. However, most physical, and chemical processes in electrochemical systems are shown to be distinguishable by their distinct characteristic time constant. Electrochemical impedance spectroscopy (EIS) can therefore be a valuable tool to distinguish between internal processes within batteries based on their frequency response2–4. Numerical approaches for understanding battery systems have long been explored by researchers in academia and industry alike2,4,5. Generally, it is computationally expensive to develop a high fidelity multiscale and multiphysics model with high predictive capability that can estimate critical transport parameters and material decay. Thus, model development traditionally starts with simplistic models where more physics is added as per requirements. Many approaches to mathematical modelling of the battery at different length scales and complexity are available today6. The impedance response of the battery can also be simulated coupled with various other parameters using the battery models7. Basic equivalent circuit models of the battery are commonly used for this but they suffer from lack of physical interpretability and model degeneracy8. The impedance response based on models are obtained in a physics-based model by linearizing the non-linear models and transforming equations in the time-domain into the frequency domain5,9. This generally is achieved by applying a Laplace transform to the system of linearized equations. Now, based on the complexity of the model, these equations can be solved analytically or after separating the real and imaginary parts for numerical simulation. Therefore, there are varied solution strategies appropriate for individual battery models that depend on underlying scale and physics involved. Through this work we aim to comprehensively compile these solution strategies and present the best approach for the individual electrochemical model based on criteria such as faster convergence times and error minimization. References: R. S. Robinson, INTELEC, Int. Telecommun. Energy Conf., 654–661 (1996). M. Gaberšček, Nat. Commun., 12, 19–22 (2021). J. Xu, C. C. Mi, B. Cao, and J. Cao, J. Power Sources, 233, 277–284 (2013). S. E. Li, B. Wang, H. Peng, and X. Hu, J. Power Sources, 258, 9–18 (2014). J. P. Meyers, M. Doyle, R. M. Darling, and J. Newman, J. Electrochem. Soc., 147, 2930 (2000). V. Ramadesigan et al., J. Electrochem. Soc., 159, R31–R45 (2012). D. Andre et al., J. Power Sources, 196, 5349–5356 (2011). S. Fletcher, J. Electrochem. Soc., 141, 1823–1826 (1994). M. Pathak et al., J. Electrochem. Soc., 165, A1324–A1337 (2018).
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Sheelam, Anjaiah, Dalton Lee Glasco e Jeffrey Gordon Bell. "Lorentz-Force-Mediated Zn Electrodeposition and Br- Ion Convection for Improved Performance in Aqueous Zn-Br2 Static Batteries". ECS Meeting Abstracts MA2022-01, n. 1 (7 luglio 2022): 17. http://dx.doi.org/10.1149/ma2022-01117mtgabs.
Abstract (sommario):
Redox flow batteries are one of the prominent electrochemical energy storage devices with large-scale storage and high energy density.1 The highly reversible Zn/Zn2+ (-0.76 V vs. RHE) and Br-/Br2 (1.08 V vs. RHE) redox couple have been employed in Zn-Br2 flow batteries (1.84 V vs. RHE). However, the dendritic growth of Zn electrodeposits during the repetitive discharge process triggers an internal short-circuit between the anode and the cathode.1 Besides this, cross-diffusion of the highly soluble Br- (Br3 -) ion causes a severe self-discharge of the system and reduced cycle life.2 Additives and ion-selective membranes have been employed to mitigate these challenges for improved cycle life and coulombic efficiency in Zn-Br2 batteries.3 Here, we fabricate an aqueous Zn-Br2 static battery with internally contained and moderate magnetic fields, (~ 30, 40, 50 and 60 mT) at the anode and cathode by incorporating 1 mm thick Nd permanent magnets. A solid complex of tetrapropylammonium tribromide was supported on activated carbon and employed as the positive electrode. Introducing a magnetic field can generate the Lorentz force (acting on Br- and Zn2+ ions), and create a controllable magnetohydrodynamic mass transport during the charge-discharge processes. Among the various magnetic fields, ~50 mT resulted in the highest coulombic efficiency (99 % for 100 cycles) and suppressed Zn dendritic growth. To rationalize the effect of magnetic fields on the efficiency and cycle life, Raman analysis, X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry (for the calculation of diffusion coefficient of Br- ion) are performed on the positive and negative electrodes of Zn-Br2 battery. References: (1) Z. Yuan, X. Liu, W. Xu, Y. Duan, H. Zhang, X. Li, Nat. Commun., 9 , 3731 (2018). (2) L. Gao, Z. Li, Y. Zou, S. Yin, P. Peng, Y. Shao, X. Liang, iScience, 23, 101348 (2020). (3) E. Sánchez-Díez, E. Ventosa, M. Guarnieri, A. Trovò, C. Flox, R. Marcilla, F. Soavi, P. Mazur, E. Aranzabe, R. Ferret, J . Power Sources, 481, 228804 (2021).
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Maeda, Hiromitsu. "Ion Pairs of Charged Porphyrins: Ordered Arrangement and Radical-Pair Formation". ECS Meeting Abstracts MA2023-01, n. 15 (28 agosto 2023): 1401. http://dx.doi.org/10.1149/ma2023-01151401mtgabs.
Abstract (sommario):
π-Electronic ions with appropriate geometries and peripheral substituents provide assemblies through the interactions between charged building subunits, resulting in fascinating electronic properties. Structures and properties of the assemblies can be controlled by the combined positively and negatively charged species in the assemblies.[1,2] In fact, π-electronic ion pairs comprising porphyrin-based π-electronic anions[3] have exhibited characteristic assembling modes via i π– i π interactions and resulting electronic properties such as solid-state absorption, which was correlated with the arrangement of constituent charged π-systems, and photoinduced electron transfer.[4] On the other hand, ion pairs of porphyrin–AuIII complexes as π-electronic cations, prepared with the combination of various anions including π-electronic anions, formed assemblies as crystals and thermotropic liquid crystals, whose ionic components were highly organized by i π– i π interactions (mainly electrostatic and dispersion forces).[5] Among various combinations of these porphyrin cations and anions, the “activated” ion pair of meso-EWG (electron-withdrawing group)-substituted cation and meso-EDG (electron-donating group)-substituted anion exhibited the electron transfer in the steady state according to solvent polarity, resulting in the production of the radical pair. The ESR in frozen toluene revealed the formation of a heterodiradical in a close stacking structure by the antiferromagnetic dipolar interaction and temperature-dependent spin transfer behavior.[6,7] [1] Recent reviews: (a) Haketa, Y. et al. Mol. Syst. Des. Eng. 2020, 5, 757; (b) Yamasumi, K. et al. Bull. Chem. Soc. Jpn. 2021, 94, 2252. [2] Recent reports on pyrrole-based π-electronic molecules: (a) Watanabe, Y. et al. Chem. Eur. J. 2020, 26, 6767; (b) Haketa, Y. et al. J. Am. Chem. Soc. 2020, 142, 16420; (c) Kuno, A. et al. Chem. Eur. J. 2021, 27, 10068; (d) Fujita, M. et al. Chem. Commun. 2022, 58, 9870. [3] (a) Sasano, Y. et al. Dalton Trans. 2017, 46, 8924; (b) Sasano, Y. et al. Chem. Eur. J. 2019, 25, 6712. [4] Sasano, Y.; Tanaka, H. et al. Chem. Sci. 2021, 12, 9645. [5] (a) Haketa, H. et al. iScience 2019, 14, 241; (b) Tanaka, H. et al. Chem. Asian J. 2019, 14, 2129. [6] Tanaka, H. et al. J. Am. Chem. Soc. 2022, 144, 21710. [7] The details of excited-state radical pairs: Tanaka, H. et al. to be submitted.