Dendrite-free Li-metal anode via a dual-function protective interphase layer for stable Li-metal pouch cell

Li metal is an ideal anode material for next-generation energy storage devices due to its extremely high theoretical specific capacity and the lowest negative electrochemical potential [1,2]. However, uncontrolled Li dendrite growth and the side reaction between Li metal and electrolytes have prevented its practical application in rechargeable Li metal batteries. In our contributions, artificial solid electrolyte interphase (SEI) layer and 3D current collector have been developed to address these issues [3,4]. In this presentation, we will introduce an artificial Li3PO4 SEI layer [3] fabricated by in situ reaction of polyphosphoric acid (PPA) with Li metal and its native film (Li2CO3, LiOH, and Li2O). The partial dissolution of the Li native film and formation of the SEI layer lead to a porous structure of the Li surface, thereby promoting Li dendrite formation and growth. In the ingenious design, the native film of Li metal is replaced by the stable and uniform Li3PO4 SEI layer. The artificial Li3PO4 SEI layer with thickness of 50 nm exhibits a smooth surface and a high Young’s modulus (10-11 GPa). Furthermore, the artificial Li3PO4 SEI layer is demonstrated to be stable in the electrolyte and during cycling in a Li|LiFePO4 battery system. The Li-conducting Li3PO4SEI layer can achieve uniform Li deposition, and reduce the side reaction between the Li metal and the electrolyte. Thus, the artificial SEI strategy we described is a promising route to tackle the intrinsic problems of Li metal anodes and other metal based anodes. Furthermore, we will show that Li metal anode can be accommodated in the reserved pores of the 3D current collector [4] with a submicron skeleton and high surface area, thereby suppressing the Li dendrite growth and solving the associated problems of Li metal anodes. Because of the high electroactive area of the submicron 3D structure, the 3D current collector can improve the Li plating/stripping efficiency and reduce the resistance of the Li metal anode. The utilization of the 3D architecture to accommodate the Li metal anode will highlight the importance of rational design of current collectors and reveal a new avenue for developing Li metal anodes with a long lifespan. References Y.-X. Yin, S. Xin, Y.-G. Guo, L.-J. Wan, Angew. Chem. Int. Ed. 2013, 52, 13186.W. Xu, J. L. Wang, F. Ding, X. L. Chen, E. Nasybutin, Y. H. Zhang, J. G. Zhang, Energ. Environ. Sci. 2014, 7, 513.N.-W. Li, Y.-X. Yin, C.-P. Yang, Y.-G. Guo, Adv. Mater. 2015, DOI: 10.1002/adma.201504526.C.-P. Yang, Y.-X. Yin, S.-F. Zhang, N.-W. Li, Y.-G. Guo, Nat. Commun. 2015, 6, 8058

The cycling lifespan of Li-metal batteries is compromised by the unstable solid electrolyte interphase (SEI) and the continuous Li dendrites, restricting their practical implementations. Given these challenges, establishing an artificial SEI holds promise. Herein, a trinitarian gradient interphase is innovatively designed through composite coatings of magnesium fluoride (MgF2), N-hexadecyltrimethylammonium chloride (CTAC), and polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) on Li-metal anode (LMA). Specifically, the MgF2/CTAC/PVDF-HFP SEI spontaneously forms a lithium fluoride (LiF)-rich PVDF-HFP-based SEI, along with lithium-magnesium (Li-Mg) alloy substrate as lithiophilic electronic conductor and positively charged CTAC during plating. Noticeably, the Li-Mg alloy homogenizes the distribution of electric field and reduce the internal resistance, while the electronically insulated LiF/PVDF-HFP composite SEI offers fast ion-conducting and mechanical flexibility, accommodating the volumetric expansion and ensuring stable Li-ion flux. Additionally, CTAC at the dendritic tip is pivotal for mitigating dendrites through its electrostatic shield mechanism. Innovatively, this trinitarian synergistic mechanism, which facilitates colossal granular Li deposits, constructs a dendrite-free LMA, leading to stable cycling performances in practical Li||LFP, popular Li||NCM811, and promising Li||S full cells. This work demonstrates the design of multifunctional composite SEI for comprehensive Li protection, thereby inspiring further advancements in artificial SEI engineering for alkali-metal batteries.

Electrochemical energy conversion and storage is critical for advancing vehicle electrification and sustainability of essential commodity chemicals. In pursuit of these goals, I delved progressively deeper into the foundational research of batteries and beyond: (1) pioneering novel methodologies to fundamentally understand reactive metal deposition, (2) regulating electrolyte to enhance lithium (Li) metal batteries (LMBs) performance, and (3) expanding the technology’s applicability to make impact beyond batteries.I have revealed the intrinsic morphology of electrodeposited Li metal to be a non-dendritic rhombic dodecahedron (Yuan et al. Nature 620, 86-91, 2023), which is surprisingly independent of electrolyte chemistry and current collector substrate. Li deposition is a process in which Li-ions are reduced to metallic form at the electrode, which plays a crucial role for LMBs, because the reversibility of deposition morphology directly determines the cycling performance and safety of the battery. However, the simultaneous formation of a surface corrosion film termed the solid electrolyte interphase (SEI) complicates the deposition process, which underpins our poor understanding of Li metal electrodeposition. I creatively integrated the classical electrochemical method, ultramicroelectrode geometry, and an emerging electron microscopy technique, cryogenic electron microscopy (cryo-EM), to decouple Li deposition from the SEI growth and capture the corresponding nanostructure of Li. This discovery has significant implications for LMBs, as it suggests SEI influence can be effectively mitigated to achieve desired deposition morphologies. Besides enhancing our understanding of Li deposition, I extended this finding to other reactive alkali metal, such as sodium metal that was found to exhibit the same polyhedral structure when outpacing the SEI influence. This emphasizes the applicability of my findings and opens new opportunities to explore how reactive metal deposition fundamentally proceeds without the influence of corrosion film, thereby regulating reversibility of metal deposition to optimize the performance of metal batteries.In addition to deposition morphology, the properties of the SEI also influence the performance of LMBs, as the SEI governs the transportation of Li-ion during cycling. Since the SEI formation results from electrolyte decomposition influenced by electric fields, I systematically examined effects of both electrolyte decomposition and electric fields on SEI formation, progressing from the bulk electrolyte to the electrode surface (Yuan et al. Joule 8, 3038-3053, 2024). I worked with colleagues to quantify reactions driving SEI formation and determine decomposition rates of individual components within the electrolyte, guiding us design and prioritize the decomposition of electrolyte components. Furthermore, I emphasized the importance of electric field to further fine-tune the formation of favorable SEI to improve battery performance.Looking beyond applications of Li metal in batteries, I leveraged the wealth of battery knowledge and established strategies to investigate fundamental aspects of Li metal as electrocatalyst in electrifying ammonia synthesis to help decarbonize the traditional chemical industry (Steinberg, Yuan (co-first) et al. Nature Energy 8, 138-148, 2023). I revealed key driver behind surface phenomena is the rupture of the SEI, enabling nitrogen and electrolyte to penetrate and react with Li metal to make ammonia. The insights from this work expanded our perspective of how Li metal electrodeposition can decarbonize chemical synthesis and inform our future efforts in designing better LMBs as well.

Elucidating the role of polar functional groups in fluorinated polymer artificial interphase for stable lithium anodes

Lithium metal is often deemed the “Holy Grail” of rechargeable battery technology, due to its high theoretical capacity and low electrochemical potential. However, the cascading heterogeneity from the formation of the solid-electrolyte interphase (SEI) up to the non-uniform current distribution leads to both poor efficiency via rapid consumption of active materials as well as safety issues from treacherous dendrite growth. An SEI that is ionically conductive while electrically resistive, viscoelastic, electrochemically stable, and possesses good mechanical properties is paramount for hindering these failure mechanisms. The discovery of novel approaches to producing an ideal SEI is a crucial piece to solving the lithium metal anode puzzle.One route of controlling the SEI is through interface engineering by producing a stable artificial SEI. In this work, a mixed artificial SEI was produced with aim toward improving ionic conductivity while retaining electrochemical stability and mechanical properties. This mixed SEI embraces the unavoidable surface heterogeneity, all the while preventing dendrite growth that plagues lithium metal batteries. A mixed artificial SEI, as well as a single-component artificial SEI, were produced through a simple and rapid deposition method and tested to observe their failure mechanisms compared to bare lithium.Symmetric cells (i.e., Li||Li) were utilized to isolate the failure mechanisms of these different anode treatments. The failure mechanism of the single-component artificial SEI cells shifted to failure via electrolyte consumption rather than short circuiting seen with bare lithium. This revealed that artificial interphases led to reduced dendrite propagation. Additionally, a reduction in cell potential range was observed with the mixed artificial SEI when compared to the single-component artificial SEI, as well as improved cyclability. Upon further investigation, it appears that the added component of the mixed artificial SEI, which was meant to improve the ionic conductivity, dissolved into the electrolyte upon initial exposure. This dissolution left behind a new SEI structure, theoretically producing easier ionic pathways and thus resulting in decreased cell overpotential. Dissolution was confirmed with high-resolution surface characterization techniques. Additionally, symmetric cell electrodes rinsed with solvent prior to testing retained superior cell performance. Though this dissolution should lead to increased available “hot spots”, the growth of dendrites was hindered. This work discusses the effect an artificial SEI has on failure mechanisms, as well as provides insight into the methods of producing stable, long-life lithium metal batteries. This includes a focus on how nanoscale heterogeneity effects cell-scale performance via high-resolution characterization and computational simulations.Different surface to sub-surface characterization techniques were utilized to measure properties of artificial SEIs and bare lithium. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS) provided elemental make-up and distribution, as well as morphological characteristics. X-ray photoelectron spectroscopy (XPS) provided the chemical state of surfaces, as well as sub-surfaces with the use of depth profiling. Different atomic force microscopy (AFM) techniques were used to spatially measure nanoscale properties such as work functions with the Kelvin probe technique (SKPFM) and quantifiable nanomechanical properties (QNM), as well as observe kinetic mechanisms with in-situ electrochemical methods (EC-AFM). Lastly, computational simulations from the atomistic scale via density functional theory (DFT) up to molecular dynamics (MD) were utilized to support assumptions on the reaction mechanisms derived from experimental observations. Figure 1

Lithium (Li)-metal anode has attracted extensive attention owing to its high theoretical specific capacity (3860 mAh/g), which is more than ten times to that of graphite anode (372 mAh/g). However, the notorious reactivity of Li-metal prevents their practical applications due to undesired Li dendrite growth and unstable solid electrolyte interphase (SEI) formation. Here, we developed a facile, cost-effective and one-step approach for creating an artificial Li-metal/electrolyte interface by treating Li metal anode with an electrolyte containing SnF2. As a result, the artificial SEI composed of LiF, Sn and Sn-Li alloy was formed with higher ionic conductivity and increased Young’s modulus. The higher ionic conductivity and larger Young’s modulus of the artificial layer facilitate fast Li-ion diffusion and suppress Li dendrite growth, respectively. The hybrid artificial SEI showed a synergistic effect of storing Li by a reversible Sn-Li alloy formation and Li plating underneath the SEI. The artificial SEI treated Li symmetrical cells showed outstanding plating/stripping cycles (~2325 hrs) with reduced overpotential compared to the bare Li. Coupled with a high-loading (11.88 mg.cm-2) LiNi1/3Co1/3Mn1/3O2 (NMC111) cathode, the SEI protected Li full cells exhibited remarkable performance such as longer stable cycling, higher capacity retention and higher capacity at higher rates compared to the bare Li anode.

One-pot solution coating of high quality LiF layer to stabilize Li metal anode

In this study, the artificial solid electrolyte interphase (SEI) formed on lithium metal when treated in ZnCl2 solutions is thoroughly investigated. The artificial SEI on lithium metal electrodes substantially decreases the interfacial resistance by ca. 80% and improves cycling stability in comparison to untreated lithium. The presence of a native SEI negatively affects the morphology and interfacial resistance of the artificial SEI. Increasing the ZnCl2 concentration in tetrahydrofuran (THF) (precursor solution) results in higher homogeneity of the surface morphology. Independent of the ZnCl2 concentrations, the artificial SEI is composed of Cx, CO, LiCl, Li2CO3, ZnCl2, and LixZny alloys. ZnCl2 (1 M) produces the most homogenous surface and additional surface species with carbonyl side groups. Nonetheless, the ZnCl2 concentration only has a small effect on the interfacial resistance or cycling stability. Using ethyl methyl carbonate (EMC) as the solvent significantly reduces the interfacial resistance to 7 Ω cm2, in comparison to 25 Ω cm2 for THF. The composition of the artificial SEIs varies depending on the solvent. Either way, the SEI consists of Cx LixC, LiCl, Li2CO3, ZnCl2, and LiZn alloys. The THF-based SEI additionally features ether and carbonyl groups, LiZnO, and Zn metal. For the artificial SEI formed with both solvents, the atomic percentage of the LiZn alloy increases close to the Li surface.

Artificial solid electrolyte interphase (SEI) layers have been widely regarded as an effective protection for lithium (Li) metal anodes. In this work, an artificial SEI film consisting of dense Li6.4La3Zr1.4Ta0.6O12 (LLZTO) nanoparticles and polymerized styrene butadiene rubber is designed, which has good mechanical and chemical stability to effectively prevent Li anode corrosion by the electrolyte. The LLZTO-based SEI film can not only guide Li to uniformly deposit at the interface but also accelerate the electrochemical reaction kinetics due to its high Li+ conductivity. In particular, the high Young's modulus of the LLZTO-based SEI will regulate e- distribution in the continuous Li plating/stripping process and achieve uniform deposition of Li. As a consequence, the Li anode with LLZTO-based SEI (Li@LLZTO) enables symmetric cells to demonstrate a stable overpotential of 25 mV for 600 h at a current density of 1 mA cm-2 for 1 mA h cm-2. The Li@LLZTO||LFP (LiFePO4) full cell exhibits a capacity of 106 mA h g-1 after 800 cycles at 5 C with retention as high as 90%. Our strategy here suggests that the artificial SEI with high Young's modulus effectively inhibits the formation of Li dendrites and provides some guidance for the design of higher performance Li metal batteries.

Deciphering the mechanism of concentrated electrolyte for lithium metal anode via cryogenic electron microscopy

Lithium-sulfur (Li-S) batteries promise the next-generation energy storage. However, one of the issues facing Li-S batteries is the high reactivity of the Li metal, leading to serious interfacial side reactions; the other is the dendritic Li growth that can usually breach the solid electrolyte interphase (SEI) applied for mitigating side reactions. To address these issues, we propose the indium fluoride-based artificial solid electrolyte interphase with tunable surface properties. Over the initial charging, InF3 nanoparticles coated on the Li anode surface can be lithiated to form a layer of nanoporous lithium/indium alloy (LixIn) encapsulating lithium fluoride (LiF) nanoparticles (3Li++3e-+InF3→3LiF+In) as shown in Figs. 1(a, b). The tightly anchored LixIn layer well attaches LiF on the anode surface during Li stripping/plating, while LiF with a higher Young’s modulus physically suppresses dendritic Li growth. Both LixIn and LiF provide facile adsorption towards Li atoms as well as high Li+ conductivity, inducing uniform Li plating [1-4]. In addition, both materials are stable with corrosive electrolyte containing polysulfides and shield Li anode from side reactions. Tuning the SEI surface properties via adding other metal fluorides such as BiF3 and AlF3, we further show the possibility to further enhance the Young’s modulus and flexibility for the SEI. Applying the rationally designed artificial SEI, substantial enhancement in terms of Li stripping/plating stability (Fig. 1c) and Li-S battery cyclability is achieved even using LiNO3-free electrolyte and the gas evolution arising from interfacial electrolyte decomposition is suppressed [5]. With enhanced mechanical strength and chemical stability, the metal fluoride-based artificial SEI paves a new way in developing durable and safer Li-S batteries. Key words: Li metal; artificial solid electrolyte interphase; dendrite; side reaction; metal fluoride. Acknowledgement The work described in this paper was fully supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. T23-601/17-R) Reference[1] Y. Ren, T. Zhao, M. Liu, Y. Zeng, H. Jiang, Journal of Power Sources, 361 (2017) 203-210.[2] X.Q. Zhang, X. Chen, R. Xu, X.B. Cheng, H.J. Peng, R. Zhang, J.Q. Huang, Q. Zhang, Angewandte Chemie, 129 (2017) 14395-14399.[3] M. Liu, Y. Ren, H. Jiang, C. Luo, F. Kang, T. Zhao, Nano Energy, 40 (2017) 240-247.[4] Y. Ren, T. Zhao, H. Jiang, M. Wu, M. Liu, Journal of Power Sources, 347 (2017) 136-144.[5] A. Jozwiuk, B.B. Berkes, T. Weiß, H. Sommer, J. Janek, T. Brezesinski, Energy & Environmental Science, 9 (2016) 2603-2608. Figure 1

Artificial polymer solid electrolyte interphases (SEIs) with microphase-separated structures provide promising solutions to the inhomogeneity and cracking issues of natural SEIs in lithium metal batteries (LMBs). However, achieving homogeneous ionic conductivity, excellent mechanical properties, and superior interfacial stability remains challenging due to interference from hard-phase domains in ion transport and solid-solid interface issues with lithium metal. Herein, we present a dynamic supramolecular ion-conducting poly (urethane-urea) interphase (DSIPI) that achieves these three properties through modulating the hard-phase domains and constructing a composite SEI in situ. The soft-phase polytetrahydrofuran backbone, featuring loose Li+-O coordinating interactions, ensures uniform Li+ transport. Concurrently, sextuple hydrogen bonds in the hard phase dissipate strain energy through sequential bond cleavage, thereby imparting exceptional mechanical properties. Moreover, enriched bis (trifluoromethanesulfonyl) imide anion (TFSI-) in DSIPI promotes the in situ formation of a stable polymer-inorganic composite SEI during cycling. Consequently, the DSIPI-protected lithium anode (DSIPI@Li) enables symmetric cells with exceptional cyclability exceeding 4,000 hours at an ultra-high current density of 20 mA cm-2, thereby demonstrating excellent cycling stability. Furthermore, DSIPI@Li facilitates stable operation of the pouch cells under the constraints of a high-loading LiNi0.8Co0.1Mn0.1O2 cathode and low negative/positive capacity (N/P) ratio. This work presents a powerful strategy for designing artificial SEIs and high-performance LMBs.

Among the many challenges for Li-ion batteries (LIBs) to achieve long cycle life, formation of high quality solid electrolyte interphase (SEI) is of critical importance. SEI forms on LIB anode during the initial cycles, and its properties directly impact battery life and power performance. In-depth understanding of SEI growth mechanism can provide critical parameter input for modeling and simulation, set foundation for the SEI properties and performance correlation, and lead to the ultimate effective artificial SEI or coating design to achieve satisfactory cell cycle efficiency. However, due to the nm thickness and air/moisture sensitivity of SEI, designing and performing in-situ diagnostics are technically challenging. To date, most studies on SEI properties are performed on electrodes harvested after SEI formation, and the time-dependent growth mechanism of SEI during its formation remains to be elucidated. In this talk, we will present an approximation of in-situ diagnostic method, by utilizing isotope-assisted time-of-flight secondary ion mass spectrometry (TOF-SIMS). This method is capable of obtaining time-dependent information during SEI growth, even after the growth process has completed. The model battery design includes a Cu electrode, 6Li labeled electrolyte (1M 6LiBF4 in EC:DEC 1:2) and a 7Li metal counter electrode. As SEI grows on the Cu electrode, the 6Li:7Li isotope ratio in the electrolyte decreases due to 6LiBF4 consumption. The time scale of SEI growth thus can be represented by the 6Li:7Li ratio in the SEI, and each 6Li:7Li ratio corresponds to a snapshot during SEI growth. The isotope ratio are measured with TOF-SIMS after harvesting the SEI. With this method, we have found that the SEI portion formed first (higher 6Li:7Li ratio) presents at the electrolyte/SEI interface, and the SEI formed last (lower 6Li:7Li ratio) exists at the SEI/electrode interface. These results also indicate that new SEI forms at the SEI/electrode interface. Further chemistry analyses with TOF-SIMS and XPS show that the portion formed first are mostly organic compounds while the portion formed last are mostly inorganic compounds. This method could also be applied in other fields where growth dynamics are of interest, such as investigating Li dendrite growth. Figure 1

Understanding of the electrical conduction, that is, ionic and electronic conduction, through the solid electrolyte interphase (SEI) is critical to the design of durable lithium-ion batteries (LIBs) with high rate capability and long life. It is believed that an ideal SEI should not only be an ionic conductor, but also an electronic insulator. In this study, we present a theoretical design of an artificial SEI consisting of lithium fluoride (LiF) and lithium carbonate (Li2CO3) on a LIB anode based on a newly developed density functional theory (DFT) informed space charge model. We demonstrate that the migration of lattice Li ions from LiF phase to form Li interstitials in Li2CO3 is energetically favorable near the LiF/Li2CO3 interface. At equilibrium, this interfacial defect reaction establishes a space charge potential across the interface, which causes the accumulation of ionic carriers but the depletion of electronic carriers near the LiF/Li2CO3 interface. To utilize this space charge effect, we propose a computationally designed, nanostructured artificial SEI structure with high density of interfaces of LiF and Li2CO3 perpendicular to the electrode. On the basis of this structure, the influences of grain size and volume ratio of the two phases were studied. Our results reveal that reducing the grain size of Li2CO3 in the nanostructured composite can promote ionic carriers and increase the ionic conductivity through the composite SEI by orders of magnitude. At the same time, the electronic conductivity is reduced due to electron depletion near the LiF/Li2CO3 interface. Furthermore, an optimal volume fraction that ensures high ionic and low electronic conduction was predicted.

The solid-electrolyte interphase (SEI) is a phase formed on an electrode by the decomposition of an electrolyte containing a lithium salt [1]. The SEI is thought to prevent further decomposition of the electrolyte, while the Li+ conductivity of the SEI enables the electrode reaction involving Li+. The Li metal anode has been investigated as an ideal anode for rechargeable Li batteries due to its negative electrode potential and high specific capacity. The cyclability of the Li anode is known to be related to the morphology of the Li metal during charge and discharge processes. The morphology of Li metal has been considered to be influenced by the properties of the SEI formed on Li metal. Therefore, the study of the SEI is important to improve the cyclability of the Li metal anode. We have previously reported that the SEI formation can be evaluated by monitoring the redox reaction of ferrocenium (Fc+)/ferrocene (Fc) as a redox probe [2-4]. The rate constant for Fc+/Fc is affected by the thickness of the SEI formed on an electrode. In the case of Fc, the SEI formation on a Cu electrode cannot be evaluated because the anodic dissolution of Cu occurs at a potential more negative than the redox potential of Fc+/Fc [5]. The redox potential of nickelocenium (Nc+)/nickelocene (Nc) is known to be about 0.5 V more negative than that of Fc+/Fc [6]. Therefore, it is expected to evaluate the SEI formation on a Cu electrode using Nc as a redox probe. In the present study, the evaluation of SEI formation on a Cu electrode was attempted in an ionic liquid, 1-buty-1-methylpyrrolidinium bis(fluorosulfonyl)amide (BMPFSA) containing LiFSA.An anodic and cathodic current peak were observed at –0.8 V vs. Ag|Ag(I) in the cyclic voltammogram of a Cu electrode in 0.5 M LiFSA/BMPFSA containing 10 mM Nc. The redox peaks were unchanged after keeping the electrode at –1.5 V vs. Ag|Ag(I) for 12 h, whereas some decomposition products were identified in the F 1s spectrum of a Cu electrode kept at –1.5 V vs. Ag|Ag(I) for 3 h, suggesting that the redox reaction of Nc+/Nc is so fast that the thickness of the SEI formed at this potential is insufficient to induce a peak shift [7]. On the other hand, a peak shift was observed at –2.0 V due to an increase in the growth rate of the SEI at the more negative potential. Thus, SEI formation on a Cu electrode was successfully observed using Nc as a redox probe.[1] E. Peled and S. Menkin, J. Electrochem. Soc., 164, A1703 (2017).[2] S. Kato, N. Serizawa, and Y. Katayama, J. Electrochem. Soc., 169, 076509 (2022).[3] S. Kato, N. Serizawa, and Y. Katayama, J. Electrochem. Soc., 170, 056504 (2023).[4] S. Okazaki, N. Serizawa, and Y. Katayama, Electrochemistry, 92, 043006 (2024).[5] N. Serizawa, T. Hisada, and Y. Katayama, Electrochemistry, 92, 043009 (2024).[6] S. Momose, M. L. Thomas, N. Serizawa, and Y. Katayama, PRiME 2024, L02-3825, Honolulu, Oct. 7 (2024).[7] J. D. Gribble and S. Wherland, Inorg. Chem., 29, 1130 (1990).