Ab Initio Molecular Dynamics Study on Self-Healing Solid Polymer Electrolyte for Lithium Metal Batteries

As renewable energy and battery-powered technologies become more widespread, high energy-density and high-performing batteries are required to meet society’s needs. While lithium-ion batteries have been the staple, their energy density development has been slow, and at gravimetric energy densities of around 250 Wh/kg, they are approaching their theoretical limit.1 The lithium-metal battery (LMB) is considered a next-generation battery due to high theoretical energy densities (ex: Lithium-Sulfur, 2600 Wh/kg), and lithium metal’s high gravimetric capacity (3860 mAh/g) and low reduction potential (-3.04 V vs S.H.E.). However, commercialization of LMBs has been limited due to various issues.Two properties that dictate the performance of the LMBs are: 1. The composition of the solid electrolyte interphase (SEI), an electronically conducting, yet passivating, layer at the anode-electrolyte interface, and 2. The morphology of the lithium deposited at the anode. Morphological studies focus on creating dense, low surface area, deposits that limit SEI fracturing and the formation of electronically disconnected lithium. SEI quality is improved by incorporating inorganic or anion-rich SEIs, formed from the electrolyte salt, to promote SEIs that are mechanically robust, ionically conducting, and homogeneous. Our group’s previous work aimed to improve LMB performance via both routes by growing resistive Al2O3 coatings on the copper (Cu) current collector using atomic layer deposition (ALD). Defects in the thin film create areas of low resistance that behave like ultramicroelectrodes which encourage radial diffusion of lithium ions to the nuclei promoting lateral growth and producing low surface area, dense, planar lithium deposits. Simultaneously, the Al2O3 coating’s Lewis acidic properties promote the decomposition and subsequent incorporation of inorganic electrolyte species into the SEI.We present a study of how the different interfaces present at the anode in LMBs impact SEI composition and battery performance. To hold the Li nucleation morphology at the anode constant, we deposit metal oxide films of a fixed resistance onto the Cu current collector, generating planar, low surface area, lithium deposits. This experimental design allows us to decouple the effect of the metal oxide thin film-electrolyte interface on SEI quality and battery performance from that of the lithium morphology. First, as shown in Fig. 1a, different metal oxide films of equal resistance, but different thicknesses, are grown via ALD, confirmed by measuring the first-cycle nucleation overpotential. The resistive metal oxides investigated are Al2O3, HfO2, AlHfxOy, and ZrO2. Scanning electron microscopy results indicate that all cells modified with equal resistance metal oxide films exhibit the same low surface area, dense, planar Li nucleation morphology. However, long-term cycling tests show differences in cell performance and life cycle. Subsequently, the composition of the SEI is investigated using X-ray photoelectron spectroscopy (XPS). Through XPS, an elemental atomic ratio analysis is conducted to investigate the relative number of species derived from the anion of the electrolyte versus the solvent of the electrolyte to reflect the anion-derived nature of the SEI. Additionally, high-resolution peaks are used to determine the relative abundance of high-quality SEI species such as lithium fluoride. This analysis confirms that the metal oxide thin film tunes the SEI composition. Additionally, we identify trends present between the SEI quality of the ALD-modified cell and its performance.To further investigate the thin film-electrolyte interface, a set of cells modified with binary stacked metal oxide thin films with two different stack orders were created, as shown in Fig. 1b. Investigating SEI composition and LMB performance, with the morphology fixed by the nucleation overpotential, allowed for deconvolution of the impact of the Cu-thin film interface and thin film-electrolyte interface. Both interfaces can in principle impact the battery’s function because 1. The Cu-thin film interface controls the electron transport to form Lio from Li+ ion during electrodeposition, and 2. The thin film-electrolyte interface can modulate the SEI. Our results indicated that the SEI and performance were both primarily regulated by the thin film-electrolyte interface. Based on our fixed-resistance and binary stack experimental design, we propose that modulation of the SEI composition by the metal oxide coating controls LMB performance when the Li nucleation morphology is fixed. This result suggests the potential for tuning LMB performance by careful selection of the metal oxide interfacial coating. References (1) Cheng, X.-B., et al. Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review. Chem. Rev. 2017, 117 (15), 10403–10473. https://doi.org/10.1021/acs.chemrev.7b00115.(2) Oyakhire, S. T., et al. Electrical Resistance of the Current Collector Controls Lithium Morphology. Nature Communications 2022, 13 (1), 3986. https://doi.org/10.1038/s41467-022-31507-w. Figure 1

Efficient energy storage is essential not only for the success of renewable energies, but also for many of daily society needs including communications, electronics, and medical and biomedical applications, among others. Electrochemical cells are complex systems integrated by several materials and their corresponding interfaces whose physical-chemical behavior is dominated by highly coupled mass and electron transport and chemical and electrochemical reactions. During lithium ion battery operation for example, during charge, lithium ions move in the electrolyte towards the anode surrounded by coordination spheres that may include solvent, salts, and other species such as additives. Once the solvated ion (inserted in a usually multicomponent network) reaches the anode surface, many additional events will take place because of the sequential and sometimes almost simultaneous reduction of the cation and that of the various components of the coordination shell. To characterize such complex environment, we analyze the Li ion coordination shell as a function of the distance to the electrode surface and electrode potential. We use density functional theory (DFT) and ab initio molecular dynamics (AIMD), to identify structural properties, as well as reactions and reaction mechanisms. Among the various “additional” species we consider the presence of long-chain polysulfides, that migrate in the electrolyte towards the Li metal anode in the Li-S chemistry. In this talk we will discuss physical, chemical, and electrochemical phenomena occurring at solid/electrolyte interfaces of Li-ion batteries and how the methods of first-principles computational analysis may be used to understand them and suggest strategies for practical solutions. In particular we will focus on the solid electrolyte interphase (SEI) occurring due to electrolyte reduction on or near Li anode surfaces and the role of the nature of the solvents, salts, and additives on the resultant SEI properties as well as on dendrite formation and battery performance.

Recent progress in carbon/lithium metal composite anode for safe lithium metal batteries

Lithium (Li) metal anodes have become an important component of the next generation of high energy density batteries. However, the Li metal anode still has problems such as Li dendrite growth and unstable solid electrolyte interface layer. Herein, we present a functional electrolyte additive (PANHF) successfully synthesized from acrylonitrile and hexafluorobutyl methacrylate via a polymerization reaction. With extensive analytical characterization, it is found that the PANHF can improve the reversibility and Coulombic efficiency of the Li deposition/dissolution reaction and prevent the growth of Li dendrites by forming a solid electrolyte interphase rich in organic matter on the outer layer and LiF on the inner layer. The results show that the cycling performance of the Li/Li cell was greatly improved in the electrolyte containing 0.5 wt % PANHF. Specifically, the cycling stability of more than 700 cycles was achieved at a current density of 1.0 mA cm-2. Moreover, the Li/NCM811 cell with 0.5 wt % PANHF has a higher capacity of 137.7 mA h g-1 at 1.0 C and a capacity retention of 83.41% after 200 cycles. This work highlights the importance of protecting the Li metal anode with functional bipolymer additives for next-generation Li metal batteries.

LiF-rich and self-repairing interface induced by MgF2 engineered separator enables dendrite-free lithium metal batteries

Lithium (Li) metal batteries (LMBs) are enjoying a renaissance due to the high energy densities. However, they still suffer from the problem of uncontrollable Li dendrite and pulverization caused by continuous cracking of solid electrolyte interphase (SEI) layers. To address these issues, developing spontaneously built robust polymer-reinforced SEI layers during electrochemical conditioning can be a simple yet effective solution. Herein, a robust homopolymer of cyclic carbonate urethane methacrylate is presented as the polymer matrix through an in situ polymerization method, in which cyclic carbonate units can participate in building a stable polymer-integrated SEI layer during cycling. The as-investigated gel polymer electrolyte (GPE) assembled LiCoO2 /Li metal batteries exhibit a fantastic cyclability with a capacity retention of 92% after 200 cycles at 0.5 C (1 C = 180 mAh g-1 ), evidently exceeding that of the counterpart using liquid electrolytes. It is noted that the anionic ring-opening polymerization of the cyclic carbonate units on the polymer close to the Li metal anodes enables a mechanically reinforced SEI layer, thus rendering excellent compatibility with Li anodes. The in situ formed polymer-reinforced SEI layers afford a splendid strategy for developing high voltage resistant GPEs compatible with Li metal anodes toward high energy LMBs.

Solid‐state lithium metal batteries (SSLMBs) have gained extensive attraction as one kind of next‐generation energy storage device. However, the drawbacks of flammability, low mechanical strength, and low ionic conductivity limit the further development of solid‐state polymer electrolytes (SPEs). In this work, a reactive flame‐retardant unit into the polymer framework via covalent bonding to create a nonflammable and stretchable polyurethane‐based SPEs is introduced. Meanwhile, the mechanical strength of the polymer backbone is increased by grafting a rigid benzene ring unit, which remarkably suppresses the lithium‐dendrite growth. As a result, these inflammable SPEs do not burn after contact with flames for 6 s. Furthermore, the obtained SPE expands the electrochemical stability window up to 5.1 V. Small monomers containing bromine decompose on the surface of lithium metal creating a LiBr riched solid electrolyte interface (SEI). Li|SPEs|Li symmetric battery offers a stable cycling life for more than 2100 h at 0.2 mA cm−2 and 0.2 mAh cm−2. The LiNi0.6Co0.2Mn0.2O2|SPEs|Li cell equipped with the integrated cathode delivers a 142.1 mAh g−1 capacity after 330 cycles at 0.3 C with 85.2% capacity retention.

Lithium metal batteries (LMBs) hold great promise for next-generation energy storage due to the ultrahigh theoretical capacity of lithium metal. However, an unstable solid electrolyte interphase (SEI) remains a critical challenge as these interfaces govern lithium diffusion during plating and stripping and prevent electrolyte degradation during cycling. Understanding the SEI's chemical composition and evolution is crucial for improving LMB performance.This study investigates the impact of different lithium salts on SEI formation in ether-based electrolytes using in-operando Fourier Transform Infrared (FTIR) spectroscopy. Three electrolytes were studied: 1M LiTFSI, 1M LiClO4, and 1M LiDFOB in DME: DOL. In-operando FTIR measurements were conducted on Li ||Li symmetric cells during plating and stripping at a current density of 3 mA/cm2. The results reveal distinct differences in SEI kinetics, composition, formation, and evolution depending on the salt used. In-operando FTIR in tandem with post-mortem X-ray Photoelectron Spectroscopy (XPS) reveals different compounds forming on the lithium surface. LiTFSI-based electrolytes showed an instantaneous interaction with the Li surface forming both organic and inorganic SEI components. In contrast, LiClO4 showed a delayed Li-salt interaction started after minutes into plating. The LiDFOB electrolyte resulted in an organic dominated SEI with limited inorganic compounds leading to an unstable SEI. These differences in SEI chemistry correlate with electrochemical performance, with LiTFSI exhibiting superior performance.This study provides direct spectroscopic evidence of SEI formation and evolution in LMBs, highlighting the critical role of electrolyte salt chemistry in determining interfacial properties and battery performance.

In lithium metal batteries (LMBs), electrolytes composed of salts and organic solvents play a significant role in transporting Li+ ions and creating the surface film on Li-metal anodes. Herein, the effect of methyl acetate (MA) as a co-solvent is reported, which enables the facilitated Li+ transport and formation of a robust solid electrolyte interphase (SEI) on the Li-metal anode. The symmetrical Li//Li cell tests show remarkable cycle stability of MA-based electrolytes at 3 mA/cm2 without obvious voltage fluctuation. At 5 mA/cm2, the Li//Li cells in MA-based electrolytes can still run up to 110 h with lower overpotential, compared to the cell cycled with MA-free electrolytes. Furthermore, the LMBs consisting of the Li anode and LiNi0.8Co0.15Al0.05O2 (NCA) cathode deliver the high capacity (∼200 mA h/g), good cycling stability up to 300 cycles, excellent rate capability (10 C), and low self-discharging rates (8.5%) with MA-based electrolytes. Especially, the capacity of the Li//NCA cells with MA30 electrolytes at -35 °C is as high as 144 mA h/g, which is higher than that of the cells in MA-free electrolytes. It demonstrates that the MA is beneficial for the LMB operation at high rate and low temperature.

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).

While the formation of an inorganic-rich solid electrolyte interphase (SEI) plays a crucial role, the persistent challenge lies in the formation of an organic-rich SEI due to the high solvent ratio in low-concentration electrolytes (LCEs), which hinders the achievement of high-performance lithium metal batteries. Herein, by incorporating di-fluoroethylene carbonate (DFEC) as a non-solvating cosolvent, a solvation structure dominated by anions is introduced in the innovative LCE, leading to the creation of a durable and stable inorganic-rich SEI. Leveraging this electrolyte design, the Li||NCM83 cell demonstrates exceptional cycling stability, maintaining 82.85% of its capacity over 500 cycles at 1 C. Additionally, Li||NCM83 cell with a low N/P ratio (≈2.57) and reduced electrolyte volume (30µL) retain 87.58% of its capacity after 150 cycles at 0.5 C. Direct molecular information is utilized to reveal a strong correlation between solvation structures and reduction sequences, proving the anion-dominate solvation structure can impedes the preferential reduction of solvents and constructs an inorganic-rich SEI. These findings shed light on the pivotal role of solvation structures in dictating SEI composition and battery performance, offering valuable insights for the design of advanced electrolytes for next-generation lithium metal batteries.

<p indent="0mm">Since the commercialization of lithium-ion batteries in the 1990s, lithium-ion batteries have been successfully applied in portable electronics, electric vehicles, and grid energy storage. Although current organic liquid electrolytes have high ionic conductivities, they are inherently flammable, volatile, and prone to leakage. Moreover, severe side reactions and dendrite growth on the surface of the lithium anode during the charge-discharge process can cause safety hazards, which greatly impede their applications in lithium metal batteries. Solid electrolytes, including inorganic solid electrolytes and polymer electrolytes, are regarded as effective alternatives to organic liquid electrolytes for the construction of lithium metal batteries with high energy density and safety. Among them, solid polymer electrolytes offer excellent flexibility, processability, and interfacial compatibility over inorganic solid electrolytes, and they are extraordinarily promising for lithium metal batteries with high energy density and safety. Ideal solid polymer electrolytes should have following features: (1) High ionic conductivity (&gt; <sc>10 ^–4 S cm ^–1) </sc> at room temperature; (2) high lithium ion transference number (~1) to reduce the concentration polarization and improve the rate performance of batteries; (3) intimate contact at the electrode/electrolyte interfaces; (4) wide electrochemical window <sc>(&gt;4.5 V</sc> vs. Li/Li ⁺) to match high-voltage cathodes and improve the energy density of batteries; (5) good mechanical stability to resist processing, buffer electrode volume change and inhibit dendrite growth; (6) good thermal stability to withstand environmental changes. Generally, the ionic conductivity of pure solid polymer electrolytes at room temperature is low <sc>(~10 ^–6 S cm ^–1). </sc> Researchers have tried to improve the ionic conductivities by adjusting the lithium salt concentration, such as developing “polymer-in-salt” solid electrolytes. However, increasing the concentration of lithium salt leads to the deterioration of the mechanical strength. Strategies such as developing novel lithium salts, modifying polymer matrix, and incorporating inorganic fillers into solid polymer electrolytes are proposed to promote ionic conductivities of solid polymer electrolytes. In particular, composite polymer electrolytes, fabricated by dispersing a certain amount of inorganic fillers into solid polymer electrolytes, have improved ionic conductivities without sacrificing their mechanical performances. Poor interfacial property between electrodes and electrolytes is also a critical issue for solid polymer electrolytes. On one hand, poor and uneven solid/solid contacts at the electrode/electrolyte interfaces lead to high resistance and sluggish ionic transport kinetics. Furthermore, the volume change of the positive and negative electrodes in the charge/discharge process deteriorates the interfacial contacts, blocks the ion and electron transport through the interfaces, and greatly reduces the electrochemical reaction kinetics. On the other hand, the electrochemical windows of solid polymer electrolytes are usually narrow <sc>(＜4.5 V).</sc> During cycling, redox reactions are prone to occur at the electrode/electrolyte interfaces, causing battery failure. Solid polymer electrolytes have also poor thermal and mechanical stabilities. Therefore, design and synthesis of polymer-based solid electrolytes with excellent comprehensive performances and construction of fast and stable ion transport channels at the electrolyte/electrode interfaces are of great significance for the successful development of solid-state lithium metal batteries. This paper presents a brief review of the research progress in solid polymer electrolytes from two aspects: Improving the ionic conductivities of solid polymer electrolytes and enhancing the interfacial performance at electrolyte/electrode interfaces. First, targeted optimization strategies on ionic conductivities of solid polymer electrolytes, including constructing continuously aligned ionic transport paths and shortening the ionic transport distance, are summarized. Second, interface optimization strategies, including constructing wetting interfaces and synthesizing asymmetric electrolytes, are presented to reduce the interface resistance and improve the interfacial contact. Finally, perspectives on the development of solid polymer electrolytes and high-performance solid-state lithium metal batteries are discussed, and key research directions and advanced test methods are proposed. This review may provide a comprehensive understanding and further guidance for not only the material design of solid polymer electrolytes, but also the structural design of lithium metal batteries with favorable electrochemical and interfacial performances.

Lithium metal batteries, directly utilizing lithium metal as an anode, are promising as new-generation energy storage devices, and the characteristics of the solid electrolyte interphase (SEI) layer are critical to battery operation. However, the roles of electrolyte compositions on the structure and thickness of the passivating SEI film at the atomistic level have been previously overlooked, resulting in poor understanding of SEI characteristics. In this study, the formation of the native SEI layer on lithium metal electrode and various electrolyte composition is scrutinised using ReaxFF molecular dynamics (MD) simulations. The study successfully identifies different layers of the SEI film using charge distribution as a tool. The decrease in lithium density and the increase in the charge states of oxidised lithium atoms contribute to the identification of an inner layer and a transition layer within the previously known interface layer, as well as the sparse layer. Additionally, different reaction schemes are observed through the analysis of ratio between consumed lithium atoms and electrolyte molecules. Furthermore, results show the lithium salt concentration effects in suppressing the growth of the SEI between the lithium anode and the liquid electrolyte, and inhibiting the formation of key SEI components. This work provides new insights into the nature of SEI surface chemistry and potentially facilitates the design of artificial SEI layers and optimal electrolyte solutions.

In the development of the next-generation safe solid-state supercapacitors with high energy density, durability, and flexibility, the synthesis of high ion-conducting solid-state electrolytes with electrochemical and mechanical stabilities is a great challenge. Solid-state polymer electrolytes (SSPEs) are of great interest as materials in energy storage devices because ion-conducting SSPEs enable good adherence to electrodes and excellent processability for being made into a thin film. The key challenge facing the SSPE development for all-solid-state supercapacitors is to achieve high mechanical performance without sacrificing the requisite ionic conductivity. To overcome the issue, we synthesized networked polymer electrolytes in both aqueous- and non-aqueous forms, using UV or thermal cross-linking methods. The aqueous versions comprise nanohybrid polymer electrolytes (NPEs), salt-in-polyampholoytes (SIPAs), and triple-network polymer electrolytes (TNPEs). Meanwhile, the non-aqueous type features branched network structures endowed with hierarchical nano-canyon characteristics. To tune and understand the SSPE physical and electrochemical properties, the effects of electrolyte type and concentration on morphologic, dielectric, and mechanical properties were thoroughly explored by microstructural, dielectric relaxation, and mechanical measurements. We found that intermolecular interactions within the electrolyte play a vital role in the formation of a nanoscale ion channel confined in the polymer matrix, allowing for a simultaneous increase in the ionic conductivity and mechanical modulus. Tuning the SSPE morphology can also control the microscopic ion migration rate as well as the macroscopic flexibility of the SSPE. To further introduce multifunctional properties, nanocomposite SSPEs were also prepared by combining aqueous SSPEs with inorganic nanoparticles, and their physical properties were investigated using dielectric relaxation spectroscopy, oscillatory shear, and DFT calculation. The principal focus of this presentation is on the insight about our understanding of ion and polymer dynamics of the SSPEs for high-performance supercapacitors.

The formation of inactive lithium by side reactions with liquid electrolyte contributes to cell failure of lithium metal batteries. To inhibit the formation and growth of inactive lithium, further understanding of the formation mechanisms and composition of inactive lithium are needed. Here we study the impact of gas producing reactions on the formation of inactive lithium using ethylene carbonate as a case study. Ethylene carbonate is a common electrolyte component used with graphite-based anodes but is incompatible with Li metal anodes. Using mass spectrometry titrations combined with 13C and 2H isotopic labeling, we reveal that ethylene carbonate decomposition continuously releases ethylene gas, which further reacts with lithium metal to form the electrochemically inactive species LiH and Li2C2. In addition, phase-field simulations suggest the non-ionically conducting gaseous species could result in an uneven distribution of lithium ions, detrimentally enhancing the formation of dendrites and dead Li. By optimizing the electrolyte composition, we selectively suppress the formation of ethylene gas to limit the formation of LiH and Li2C2 for both Li metal and graphite-based anodes.