Solid Electrolyte Interphase Components Research Articles

Tuning solvation behavior within electric double layer via halogenated MXene for reliable lithium metal batteries

Solid electrolyte interphase (SEI)/electrolyte interface is critical in determining the lithium (Li) plating/stripping behavior. The solvation structure of Li-ion is well understood in the bulk electrolyte. Still, the mechanism of how SEI components affect the Li-ion solvation structure and desolvation energy barrier at the SEI/electrolyte interface is still unclear. Herein, Ti3C2 Maxine with single halogenated terminations (−Cl, −Br, −I) are synthesized and used as a model system, because their surface terminations induce a double halide-rich SEI formation (LiF and LiCl/LiBr/LiI). We examine the influence of the interaction strength between different Li halides and Li-ion on coordination number of Li ions and distribution of Li ions within the inner Helmholtz plane (IHP). A solvation sheath with a low solvent coordination number forms near the IHP of the LiBr interphase, improving the kinetics of Li deposition. Accordingly, half-cells utilising Li-carbon fiber/Ti3C2Br2 electrodes exhibit a long lifespan of 12,000 h (1 mA cm−2, 1 mAh cm−2). A pouch cell comprising Li-carbon fiber/Ti3C2Br2 anode and LiFePO4 cathode displays a capacity retention rate of 97 % after 300 cycles even at a low negative to positive electrode capacity ratio of 2.26. Our research provides crucial principles for the design of SEI components in Li metal batteries.

Exploring the Impact of In Situ-Formed Solid-Electrolyte Interphase on the Cycling Performance of Aluminum Metal Anodes.

Unwanted processes in metal anode batteries, e.g., non-uniform metal electrodeposition, electrolyte decomposition, and/or short-circuiting, are not fully captured by the electrolyte bulk solvation structure but rather defined by the electrode-electrolyte interface and its changes induced by cycling conditions. Specifically, for aluminum-ion batteries (AIBs), the role of the solid-electrolyte interphase (SEI) on the Al0 electrodeposition mechanism and associated changes during resting or cycling remain unclear. Here, we investigated the current-dependent changes at the electrified aluminum anode/ionic liquid electrolyte interface to reveal the conditions of the SEI formation leading to irreversible cycling in the AIBs. We identified that the mechanism of anode failure depends on the nature of the counter electrode, where the areal capacity and cycling current for Al0 electrodeposition dictates the number of successful cycles. Notwithstanding the differences behind unstable aluminum anode cycling in symmetrical cells and AIBs, the uniform removal of electrochemically inactive SEI components, e.g., oxide-rich or solvent-derived organic-rich interphases, leads to more efficient cycling behavior. These understandings raise the importance of using specific conditioning protocols for efficient cycling of the aluminum anode in conjugation with different cathode materials.

Highly Stable Sodium Metal Batteries Enabled by Manipulating the Fluorinated Organic Components of Solid‐Electrolyte‐Interphase

AbstractNa metal batteries (NMBs) stand at the forefront of advancing energy storage technologies, but are severely hampered by Na dendrite issues, especially when using carbonate electrolytes. Suppressing the growth of Na dendrites through constructing NaF‐rich solid‐electrolyte‐interphase (SEI) is a commonly‐used strategy to prolong the lifespan of NMBs. In contrast, fluorinated organic SEI components are often underutilized. Inspired by unveiling the adsorption configuration of fluorinated organic compounds on the surface of Na metal, an optimized SEI architecture for stabilizing NMBs is proposed by investigating the C4H9SO2F‐/C4F9SO2F‐treated Na metal anodes. It is revealed that the SEI built on a fluorinated inorganic/organic hybrid layer exhibit favorable Na passivation capability, significantly improving Na deposition behavior. As a result, the NMB with a high‐loading cathode (15 mg cm−2) and a negative/positive capacity ratio (N/P) ratio of 4 shows a long‐term life span over 1000 cycles with 92.8% capacity retention at 2 C. This work opens a new pathway for developing robust and high‐energy‐density NMBs.

Uncovering Reduction Mechanisms of Fluoroethylene Carbonate

Energy storage plays an integral role in climate change mitigation, given that many promising alternatives to fossil fuel-based technologies rely on intermittent energy sources like the sun or wind. Particularly, lithium metal batteries (LMBs) are a promising technology due to lithium’s high theoretical specific capacity and low reduction potential, which can result in batteries with energy densities surpassing current state of the art lithium-ion batteries.1 Electrolyte design is a key strategy to improve the cycling stability and Coulombic efficiency of LMBs, where the highly reductive lithium metal anode reacts with the electrolyte during cycling, resulting in capacity loss. These reactions form a solid electrolyte interphase (SEI), and many successful electrolyte engineering strategies have involved tuning the SEI to be mechanically and chemically stable to prevent further reactions.In this research, we focus on fluoroethylene carbonate (FEC), a highly effective electrolyte solvent in LMBs.2 Although prior research has illuminated key reduction products of FEC2,3, including lithium fluoride (LiF), there remains a gap in understanding regarding the mechanism by which FEC and other similar fluorinated solvents are reduced to form an SEI. Furthermore, recent research has demonstrated that a preformed SEI comprised solely of LiF breaks down during cycling, illustrating that bulk chemical and mechanical properties of SEI components may not translate to their function within the SEI.4 In this work, we employ electron paramagnetic resonance (EPR) spectroscopy to study intermediate generation during FEC reduction. We pursued both a chemical reduction using lithium naphthalenide and an electrochemical approach to reduce FEC. The use of EPR with spin traps enables insight into the radical species formed during FEC reduction, which we hypothesize are precursors to cross-linked polymer networks that are key to a high performing SEI. Here, we employed conventional post-mortem SEI analysis like X-ray Photoelectron Spectroscopy (XPS) in addition to EPR to clarify reduction mechanisms of FEC and form a framework for studying electrolyte reduction intermediates. Ultimately, this approach affords insight into electrolyte breakdown mechanisms to form an effective SEI which can both accommodate volume expansion and inhibit parasitic electrolyte consumption. This will guide electrolyte design for high Coulombic efficiency LMBs in the future.References K. G. Gallagher et al., Energy Environ. Sci., 7, 1555–1563 (2014).X.-Q. Zhang, X.-B. Cheng, X. Chen, C. Yan, and Q. Zhang, Advanced Functional Materials, 27, 1605989 (2017).Y. Jin et al., J. Am. Chem. Soc., 139, 14992–15004 (2017).M. He, R. Guo, G. M. Hobold, H. Gao, and B. M. Gallant, Proceedings of the National Academy of Sciences, 117, 73–79 (2020).

Understanding Organic Components of Solid Electrolyte Interphase on the Lithium Metal Anode

Lithium ion batteries have become the dominant form of energy storage used in consumer electronics and, recently, electric vehicles. However, high costs have prevented widespread deployment of lithium ion batteries for applications other than portable electronics, and the safety issues associated with liquid organic electrolytes remain to be addressed. In order to enable the greater utilization of electric vehicles, allow for grid scale energy storage, and meet the demands of new electronic applications, new materials for high energy density batteries must be developed. High capacity electrode materials like lithium metal have the potential to facilitate these technologies, but lithium metal electrodes are presently limited by significant side reactions, poor quality deposition, and the potential to form hazardous dendrites. Therefore, it is important to develop a clear understanding of the surface reactivity and growth behavior of the lithium metal at the interface with the electrolyte in order to enable stable long-term cycling.The products that form as a result of electrolyte decomposition reactions at the electrode interface are known to be extremely important in determining the final cell performance, yet characterizing the organic components of the solid electrolyte interphase (SEI) proves to be challenging with typical techniques. In this presentation we will discuss a combination of in operando and ex situ techniques developed in efforts to more comprehensively characterize the reaction intermediates and organic SEI products of electrolyte reduction reactions. Specifically, we employ electron paramagnetic resonance (EPR) spectroscopy to identify radical intermediates and clarify electrolyte reduction mechanisms. Furthermore, SEI product formation with respect to electrochemical potential and time will be described using data obtained from in operando ATR-FTIR. ATR-FTIR is a powerful method for characterizing organic species, but typical materials such as Ge, Si, and ZnSe react with lithium metal during deposition. In this talk, the development of a diamond based operando cell and its application to the characterization of organosulfur and fluorinated electrolytes will be discussed. With the understanding developed from these two techniques we provide new insights into the formation and chemical nature of SEI components that promote stable cycling of lithium metal electrodes.

Formation and Cycling of Microscale Silicon Anodes at Elevated Temperatures with FEC-Based and EC-Based Electrolytes

Silicon is a promising candidate to replace graphite (372 mAh g-1) as anode material in lithium-ion batteries (LIBs) due to its high theoretical gravimetric capacity of 3589 mAh g-1.1 Graphite is already partially substituted by silicon in commercial battery applications in order to increase the energy density of LIBs.2 However, a complete transition to silicon is still hindered by the extreme volume expansion of up to 300% upon complete electrochemical lithiation to Li15Si4.3 This causes particle cracking, electrical contact loss of active material, and the continuous (re-)formation of the solid electrolyte interphase (SEI) on the newly formed surface, leading to a continuous loss of cyclable lithium and a fast capacity fading of the cell.One approach to mitigate Si particle cracking is the partial lithiation of microscale silicon, limiting the capacity to ~1200 mAh g-1, i.e., one-third of the theoretical capacity, enabling a cycle-life of more than 200 cycles before reaching 80% state-of-health (SOH).4 While electronic disconnection of lithiated silicon contributes to the overall cyclable lithium losses, the continuous formation of the SEI remains one of the major challenges that limit the lifetime.5 Fluoroethylene carbonate (FEC) has been shown to be one of the most suitable additives for silicon-containing cells to ensure the formation of a suitable SEI and comparably stable cycling performance.6,7 However, especially at elevated temperatures, FEC decomposes to form vinylene carbonate and hydrogen fluoride, which is detrimental to the SEI.8 This study investigated temperature-dependent cycle-life stability of microscale-silicon dominant anodes with EC-based and FEC-based electrolytes at room and elevated temperature. The electrodes consist of 70% silicon (Wacker Chemie AG) with an LiPAA binder (8%) and conductive carbon (2%). Additionally, graphite (8% KS6L, Imerys) was added to enhance the electronic conductivity, whereby within the operating voltage range of the anode, only a minor capacity of the graphite is used. As electrolytes, either 1 M LiPF6 in EC:DEC 1:2 v:v (EC-based) or 1 M LiPF6 in FEC:DEC 2:8 v:v (FEC-based) were used. Full-cells were cycled with a nickel-rich transition metal oxide cathode active material (LiNi0.83Co0.12Mn0.05O2 (NCM831205), BASF SE) based cathode at 25 °C and 45 °C. As shown in Figure 1, cycling in coin cells revealed the expected decreased cycle-life of cells with the FEC-based electrolyte at 45 °C (light blue) compared to 25 °C (dark blue).8 However, cycling cells with the FEC-free, EC-based electrolyte (green) at elevated temperatures, showed the opposite trend. The cycle-life until 80% SOH increased by 110 cycles (+100%), surpassing that of the cells with the FEC-based electrolyte at 45 °C. The charge-averaged mean voltages for both charge and discharge were investigated to identify the main failure mechanisms. This allowed us to differentiate between the loss of cyclable lithium and internal cell resistance build-up.To better understand the contributions of anode and cathode to capacity fading, we assembled Swagelok® T-Cells with the same cell chemistry and cycled them analogously. While the resistance of the cathode remained nearly constant over the whole course of cycling, the resistance of the anode showed an increase with decreasing cell capacity. Furthermore, online electrochemical mass spectrometry (OEMS) was performed to determine the gases evolved during formation with the EC-based electrolyte at 25 °C and 45 °C. This allowed us to gain insights into the overall SEI formation mechanism and to differentiate the formation of suitable SEI components.

Decomposition Mechanism of Lithium Methyl Carbonate with Electrolyte in the Solid Electrolyte Interphase to Elucidate the Early Stages of Thermal Runaway in Lithium-Ion Batteries

With the growing demand for electric vehicles, the safety of lithium-ion batteries has been greatly emphasized. Thermal runaway caused by the continuous side reactions inside the battery makes it difficult to extinguish fires caused by abnormal activity. The temperature at which a typical thermal runaway begins is around 100°C, the temperature at which several elements in the solid electrolyte interphase (SEI) layer on the anode surface experience thermal decomposition reactions (causing gas generation and heat production). Therefore, to understand the first stage of thermal runaway and increase battery safety, it is necessary to describe the thermal decomposition process of the SEI layer.To investigate the thermal decomposition process of the SEI layer, it is necessary to understand the various organic components. During the initial charging phase, the reduction reaction between the lithium ions and the electrolyte produces a series of components that make up the SEI layer. On the surface of the anode active material, the SEI layer is a thin layer with an overall thickness of 10-50 nm. It is composed of various organic (inner layer) and inorganic (outer layer) elements. Under thermal stress, the unstable organic SEI layer decomposes into an inorganic SEI layer due to its low stability in the presence of heat and gas generation, which is mostly caused by the decomposition of lithium carbonate (ROCOOLi). It is important to note that the most used electrolytes in batteries today are ethylene carbonate and ethyl methyl carbonate (EMC) dissolved in salts based on lithium hexafluorophosphate. Due to the application of EMC, lithium methyl carbonate (LMC) accounts for more than 50% of the SEI layer in the ROCOOLi compounds.This study used both theoretical and experimental techniques to fully elucidate the pyrolysis process of high-purity synthesized LMC with the electrolyte. First, LMC was chemically synthesized using a nucleophilic substitution reaction. Then, in-situ thermogravimetry analysis (TGA)-mass spectrometer(MS), attenuated total reflectance (ATR)- fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR) results along with bond dissociation energy (BDE)/spectral analysis/energy diagrams obtained by density functional theory (DFT) calculations were analyzed to propose the elementary reaction steps involved in the pyrolysis reaction. We propose six elementary reaction steps for the pyrolysis reaction of LMC. To verify the validity of the proposed basic reaction mechanisms, chain reactions involving radicals generated during pyrolysis were finally calculated using GRI-MECH 3.0, and the calculated results were compared with the composition of the actual gas. We hope to utilize the techniques used in this study to obtain the reaction steps of additional SEI components (LEMC, Li2CO3, etc.). The precise mechanisms obtained through modeling studies can be used to predict the self-heating phase of thermal runaway and to develop materials that can stop the SEI decomposition reaction.

Upcycling of Graphite Anodes via Tailored Solvent Treatment

To achieve a truly closed-loop direct recycling process for lithium-ion batteries, all component materials must be recovered. To date, direct recycling method development has primarily focused on the high-value transition-metal cathode materials, while the inherently lower-value graphite has been challenging to recover in a cost-effective manner. However, end-of-life graphite contains a unique engineered value due to the presence of the solid electrolyte interphase (SEI). Growth of the SEI during the cell’s active lifetime stabilizes the electronically reactive graphite surface through an irreversible consumption of Li, and thus necessitates both excess lithiation of the cathode and a costly and time-intensive formation procedure during manufacturing. An optimized pre-formed SEI that capitalizes on existing SEI components from end-of-life batteries has the potential to significantly reduce cathode lithiation requirements and eliminate the critical bottleneck of formation cycling during cell remanufacturing. Further, retaining Li at the anode obviates the need for a separate Li leaching and recovery step, improving the overall efficiency of the direct recycling line. In this work, we present a novel approach to “upcycling” spent graphite through use of tailored chemical treatment to remove adverse (i.e., highly resistive and/or poorly passivating) SEI species while retaining beneficially passivating components. We have explored a rational set of solvents spanning a range of polarity, proticity, and molecular size to evaluate structure-property-performance relationships between applied solvent(s), removed and remaining SEI species, and electrochemical response of the resulting graphite product. Further, we have developed and optimized a robust and holistic analysis procedure that couples symmetric-cell electrochemical testing, multi-modal materials characterization, and advanced electrochemical modeling. These analysis results inform a set of correlative metrics for graphite performance relative to both solvent properties and upcycled SEI composition. We demonstrate effective tunability in the residual SEI composition by varying solvent identity and concentration, and report on several promising solvent systems that achieve comparable performance to pristine graphite. Figure 1

Lithium Hydride in the Solid Electrolyte Interphase of Lithium‐Ion Batteries as a Pulverization Accelerator of Silicon

AbstractAs a highly promising next‐generation high‐specific capacity anode, the industrial‐scale utilization of micron silicon has been hindered by the issue of pulverization during cycling. Although numerous studies have demonstrated the effectiveness of regulating the inorganic components of the solid electrolyte interphase (SEI) in improving pulverization, the evolution of most key inorganic components in the SEI and their correlation with silicon failure mechanisms remain ambiguous. This study provides a clear and direct correlation between the lithium hydride (LiH) in the SEI and the degree of micron silicon pulverization in the battery system. The reverse lithiation behavior of LiH on micron silicon during de‐lithiation exacerbates the localized stress in silicon particles and contributes to particle pulverization. This work successfully proposes a novel approach to decouple the SEI from electrochemical performance, which can be significant to decipher the evolution of critical SEI components at varied battery anode interfaces and analyze their corresponding failure mechanisms.

Lithium Hydride in the Solid Electrolyte Interphase of Lithium-Ion Batteries as a Pulverization Accelerator of Silicon.

As a highly promising next-generation high-specific capacity anode, the industrial-scale utilization of micron silicon has been hindered by the issue of pulverization during cycling. Although numerous studies have demonstrated the effectiveness of regulating the inorganic components of the solid electrolyte interphase (SEI) in improving pulverization, the evolution of most key inorganic components in the SEI and their correlation with silicon failure mechanisms remain ambiguous. This study provides a clear and direct correlation between the lithium hydride (LiH) in the SEI and the degree of micron silicon pulverization in the battery system. The reverse lithiation behavior of LiH on micron silicon during de-lithiation exacerbates the localized stress in silicon particles and contributes to particle pulverization. This work successfully proposes a novel approach to decouple the SEI from electrochemical performance, which can be significant to decipher the evolution of critical SEI components at varied battery anode interfaces and analyze their corresponding failure mechanisms.

Thermal decomposition mechanism of lithium methyl carbonate in solid electrolyte interphase layer of lithium-ion battery

To predict the early stages of thermal runaway and improve the safety of lithium-ion batteries, it is necessary to examine the elementary reaction steps for the thermal decomposition of individual solid electrolyte interphase (SEI) components. This study elucidates a detailed decomposition mechanism of lithium methyl carbonate (LMC) which is one of SEI components and accounts for the majority of SEI components formed in commercial electrolytes. The detailed reaction mechanism for the thermal decomposition of LMC is proposed based on the in-situ/ex-situ experiments and density functional theory calculations. LMC underwent six reactions before finally converting to Li2CO3 at 300 °C. To supplement the reliability of the proposed reaction mechanism, the actual gas composition measured using mass spectrometry (MS) are compared with the chain reactions of radicals generated through the thermal decomposition reactions, which is calculated using GRI-MECH 3.0, a gas-phase reaction mechanism. The methodology proposed in this study can be used both for analyzing the reaction mechanisms of different SEI components and their coupling effects with the electrolyte in the future. Understanding these reaction mechanism sets will help us to understand the degradation reactions of real complex SEI and the initial self-heating stage during thermal runaway.

Inorganic Composition Modulation of Solid Electrolyte Interphase for Fast Charging Lithium Metal Batteries.

The solid electrolyte interphase (SEI) with lithium fluoride (LiF) is critical to the performance of lithium metal batteries (LMBs) due to its high stability and mechanical properties. However, the low Li ion conductivity of LiF impedes the rapid diffusion of Li ions in the SEI, which leads to localized Li ion oversaturation dendritic deposition and hinders the practical applications of LMBs at high-current regions (>3 C). To address this issue, a fluorophosphated SEI rich with fast ion-diffusing inorganic grain boundaries (LiF/Li3P) is introduced. By utilizing a sol electrolyte that contains highly dispersed porous LiF nanoparticles modified with phosphorus-containing functional groups, a fluorophosphated SEI is constructed and the presence of electrochemically active Li within these fast ion-diffusing grain boundaries (GBs-Li) that are non-nucleated is demonstrated, ensuring the stability of the Li || NCM811 cell for over 1000 cycles at fast-charging rates of 5 C (11mA cm-2). Additionally, a practical, long cycling, and intrinsically safe LMB pouch cell with high energy density (400Wh kg-1) is fabricated. The work reveals how SEI components and structure design can enable fast-charging LMBs.

Catalytic role of in-situ formed C-N species for enhanced Li2CO3 decomposition

Sluggish kinetics of the CO2 reduction/evolution reactions lead to the accumulation of Li2CO3 residuals and thus possible catalyst deactivation, which hinders the long-term cycling stability of Li-CO2 batteries. Apart from catalyst design, constructing a fluorinated solid-electrolyte interphase is a conventional strategy to minimize parasitic reactions and prolong cycle life. However, the catalytic effects of solid-electrolyte interphase components have been overlooked and remain unclear. Herein, we systematically regulate the compositions of solid-electrolyte interphase via tuning electrolyte solvation structures, anion coordination, and binding free energy between Li ion and anion. The cells exhibit distinct improvement in cycling performance with increasing content of C-N species in solid-electrolyte interphase layers. The enhancement originates from a catalytic effect towards accelerating the Li2CO3 formation/decomposition kinetics. Theoretical analysis reveals that C-N species provide strong adsorption sites and promote charge transfer from interface to *CO22− during discharge, and from Li2CO3 to C-N species during charge, thereby building a bidirectional fast-reacting bridge for CO2 reduction/evolution reactions. This finding enables us to design a C-N rich solid-electrolyte interphase via dual-salt electrolytes, improving cycle life of Li-CO2 batteries to twice that using traditional electrolytes. Our work provides an insight into interfacial design by tuning of catalytic properties towards CO2 reduction/evolution reactions.

Li3PO4-Enriched SEI on Graphite Anode Boosts Li+ De-Solvation Enabling Fast-Charging and Low-Temperature Lithium-Ion Batteries.

Li+ de-solvation at solid-electrolyte interphase (SEI)-electrolyte interface stands as a pivotal step that imposes limitations on the fast-charging capability and low-temperature performance of lithium-ion batteries (LIBs). Unraveling the contributions of key constituents in the SEI that facilitate Li+ de-solvation and deciphering their mechanisms, as a design principle for the interfacial structure of anode materials, is still a challenge. Herein, we conducted a systematic exploration of the influence exerted by various inorganic components (Li2CO3, LiF, Li3PO4) found in the SEI on their role in promoting the Li+ de-solvation. The findings highlight that Li3PO4-enriched SEI effectively reduces the de-solvation energy due to its ability to attenuate the Li+-solvent interaction, thereby expediting the de-solvation process. Building on this, we engineer Li3PO4 interphase on graphite (LPO-Gr) anode via a simple solid-phase coating, facilitating the Li+ de-solvation and building an inorganic-rich SEI, resulting in accelerated Li+ transport crossing the electrode interfaces and interphases. Full cells using the LPO-Gr anode can replenish its 80 % capacity in 6.5 minutes, while still retaining 70 % of the room temperature capacity even at -20 °C. Our strategy establishes connection between the de-solvation characteristics of the SEI components and the interfacial structure design of anode materials for high performance LIBs.

Li3PO4‐Enriched SEI on Graphite Anode Boosts Li+ De‐Solvation Enabling Fast‐Charging and Low‐Temperature Lithium‐Ion Batteries

AbstractLi+ de‐solvation at solid‐electrolyte interphase (SEI)‐electrolyte interface stands as a pivotal step that imposes limitations on the fast‐charging capability and low‐temperature performance of lithium‐ion batteries (LIBs). Unraveling the contributions of key constituents in the SEI that facilitate Li+ de‐solvation and deciphering their mechanisms, as a design principle for the interfacial structure of anode materials, is still a challenge. Herein, we conducted a systematic exploration of the influence exerted by various inorganic components (Li2CO3, LiF, Li3PO4) found in the SEI on their role in promoting the Li+ de‐solvation. The findings highlight that Li3PO4‐enriched SEI effectively reduces the de‐solvation energy due to its ability to attenuate the Li+‐solvent interaction, thereby expediting the de‐solvation process. Building on this, we engineer Li3PO4 interphase on graphite (LPO−Gr) anode via a simple solid‐phase coating, facilitating the Li+ de‐solvation and building an inorganic‐rich SEI, resulting in accelerated Li+ transport crossing the electrode interfaces and interphases. Full cells using the LPO−Gr anode can replenish its 80 % capacity in 6.5 minutes, while still retaining 70 % of the room temperature capacity even at −20 °C. Our strategy establishes connection between the de‐solvation characteristics of the SEI components and the interfacial structure design of anode materials for high performance LIBs.

Characterization by NMR Spectroscopy of the SEI Layer Formed on Ti3C2 MXene Materials Prepared with Various Terminations

The nature and content of surface terminations are one of the key factors that define the electrochemical signature of the widely studied MXene materials. In this paper, the surface termination of molten salt synthesized Ti3C2Tx MXene with -O and -Cl terminations (T=Cl,O) are studied for the first time using solid state NMR technique, with respect to conventional HF synthesized Ti3C2Tx (T=F, O, OH). Both materials have been further used as negative electrode of Li-ion battery. The evolution of surface terminations during the Solid Electrolyte Interphase (SEI) layer formation was studied from the SEI components formed in both MXenes. Analysis of the NMR signal provided insights into the porous nature of SEI with LiF as main component in HF terminated MXenes. While a thick uniform formation of the SEI was observed for the molten salt synthesized Ti3C2Tx (T=Cl,O) with Li2CO3 as dominant component.

Dynamic and Reversible Blending Interface on Polyoxovanadate Electrode for High-Performance Lithium-Ion Batteries.

Solid electrolyte interphase (SEI) plays a critical role in the performance of lithium-ion batteries (LIBs). In contrast to the clear interface between the traditional consecutive electrode materials and SEI, ionic polyoxometalates (POMs) as electrode could bilaterally diffuse with SEI and form a blending interface for superior electrochemical performance. POMs have recently aroused much interest as electrode materials in LIBs due to their structural flexibility, high capacity, and cycling stability. However, the interface evolution between POM-based electrodes and SEI, which is critical for Li+ ion transportation, has rarely been explored. Herein, we choose Li10[V12B18O60H6] (LVB) as an example to investigate the formation and structural evolution of the electrode-electrolyte interface. Time-of-flight secondary ion mass spectrometry together with X-ray photoelectron spectroscopy demonstrates the evolution of a blending layer at the interface containing typical SEI components, a polyanion from LVB and a phosphate anion from decomposition products of LiPF6. In the blending layer, ion migration takes place between the P-related inorganic species and the polyanion during the Li+ insertion/extraction reaction. Such a compatible blending layer favors Li+ transportation and the reversibility of the redox reactions, as supported by a series of electrochemical analyses. This work provides detailed insights into understanding the interface evolution of the LVB electrode and demonstrates the importance of interfacial engineering to induce proper interface layers in the development of high-performance POM-based electrodes for LIBs.

Beyond LiF: Tailoring Li2O-Dominated Solid Electrolyte Interphase for Stable Lithium Metal Batteries.

The components and structures of the solid-electrolyte interphase (SEI) are critical for stable cycling of lithium metal batteries (LMBs). LiF has been widely studied as the dominant component of SEI, but Li2O, which has a much lower diffusion barrier for Li+, has rarely been investigated as the dominant component of SEI. The effect of Li2O-dominated SEI on electrochemical performance still remains elusive. Herein, an ultrastrong coordinated cosolvation diluent, 2,3-difluoroethoxybenzene (DFEB), is designed to modulate solvation structure and tailor Li2O-dominated SEI for stable LMBs. In the DFEB-based LHCE (DFEB-LHCE), DFEB intensively participates in the first solvation shell and synergizes with FSI- to tailor an Li2O-dominated inorganic-rich SEI which is different from the LiF-dominated SEI formed in conventional LHCE. Benefiting from this special SEI architecture, a high Coulombic efficiency (CE) of 99.58% in Li||Cu half cells, stable voltage profiles, and dense and uniform lithium deposition, as well as effective inhibition of Li dendrite formation in the symmetrical cell, are achieved. More importantly, the DFEB-LHCE can be matched with various cathodes such as LFP, NCM811, and S cathodes, and the Li||LFP full cell using DFEB-LHCE possesses 85% capacity retention after 650 stable cycles with 99.9% CE. Especially the 1.5 Ah practical lithium metal pouch cell achieves an excellent capacity retention of 89% after 250 cycles with a superb average CE of 99.93%. This work unravels the superiority of the Li2O-dominated SEI and the feasibility of tailoring SEI components through modulation of solvation structures.

Determining the Composition and Structure of a High-Performing SEI Layer for Lithium-Mediated Nitrogen Reduction to Ammonia

The industrial synthesis of ammonia (NH3) via the Haber-Bosch process has enabled mass production of fertilizer and the human population growth to 8 billion.1 NH3 also shows promise as a long-term, energy-dense fuel amenable to widespread distribution.2 However, the Haber-Bosch process operates at high temperatures and pressures in centralized facilities and accounts for 1.3% of global carbon emissions.1,2 To ensure a food-secure future and realize NH3 as a truly carbon-free fuel, we must develop an NH3 synthesis alternative that operates at ambient conditions and can be driven by renewables.One of the most promising NH3 synthesis method under mild conditions is the electrochemical, Li-mediated process (Li-NRR). In this process, Li is electrodeposited from solution and reacted with N2 to form Li3N. A proton shuttle, e.g., ethanol, protonates Li3N to form NH3.3 The electrodeposited Li forms a solid-electrolyte interphase (SEI) layer that controls N2, Li+, and H+ transport and is key to system performance. The use of fluorinated Li salts, e.g., LiBF4, have recently advanced Li-NRR system performance. Improved selectivity has been attributed to changes in the SEI layer, but evaluating SEI structure and composition remains a significant challenge.3 Neutron-based characterization methods, complementary to X-ray methods, offer unique benefits to study SEI layers containing light elements such as Li- and H; for example, an element’s neutron scattering cross section does not depend on its atomic number.4 In this work, we studied the formation of the SEI layer in-situ before and after applying -0.3 mA/cm2 in galvanostatic experiments (chronopotentiometry, CP) on a copper (Cu) working electrode. We utilized a combination of deuterated and non-deuterated solvents and proton donors to distinguish their contributions to the SEI. We found that the SEI forms two layers: a compact, lithium rich layer, and a diffuse layer with carbonaceous species (Figure 1).4 We also identified the presence of boron in the layers, indicated by neutron absorption. Finally, we observed more proton-rich species in experiments containing the non-deuterated H+ donor, corroborating previous studies that indicate that Li-ethoxide may be a major component of the diffuse SEI (Figure 1b-c).5 Compared to LiClO4-based electrolytes, the structure of these LiBF4-derived layers is consistent even after repeated current cycling, indicating a more stable SEI structure and suggesting a relationship between SEI stability and increased Li-NRR performance.References Nørskov, J. et al. DOE Roundtable Report (2016).Chang, F. et al. Advanced Materials 33, 2005721 (2021).Li, S. et al. Joule 6, 2083–2101 (2022).Blair, S.J., Doucet, M. et al. ACS Energy Lett., 7, 6, 1939-1946 (2022).Steinburg, K. et al. Nature Energy, 8, 138-148 (2023). Figure 1: (a) reflectivity curve before and after 4 mins constant applied current at -0.3 mA/cm2 (chronopoteniometry, CP) to plate Li using 1 M LiBF4 with 1 vol% ethanol, (b) resulting scattering length density (SLD) profile, and (c) schematic of layers indicated in SLD profile Figure 1

Effect of Electrolyte on Sodium-Ion Storage Behavior into Non-Graphitizable Carbon Negative Electrode

Introduction Sodium-ion batteries (SIBs) are expected to be an alternative power source to lithium-ion batteries (LIBs) because their abundant resources reduce the cost of SIBs. As the negative electrode of SIBs, non-graphitizable carbon recieves a lot of attention because it can store ions not only in the graphene interlayer but also in its internal pores.[1] By controlling the pores, it is possible to achieve larger reversible capacity of more than 400 mAh g−1.[2] While many researchers have studied non-graphitizable carbon from the viewpoint of thermodynamics, there are a few reports that pay attention to kinetic viewpoint. The kinetic viewpoint is a very important factor because it affects the rate performance of the battery.We have focused on the interfacial reactions of non-graphitizable carbon electrodes and found that the charge-transfer resistance and the activation energy of the charge-transfer reaction in SIBs were larger than those in LIBs.[3] This result and the Lewis acidity indicated that the desolvation process was not identified as the rate determining step in the charge-transfer reaction. One of the significant factors responsible for the increased resistance is the effect of the solid electrolyte interphase (SEI). Objective In this work, we used six types of electrolytes and formed SEI on the surface of non-graphitizable carbon. The interfacial reaction of non-graphitizable carbon with SEI derived from these electrolytes was investigated.In this paper, we report about the effects of SEI on the interfacial reaction between electrolyte and non-graphitizable carbon electrode. Experimental Non-graphitizable carbon heat-treated at 2273 K (HC-2000) was used as the negative electrode material. A three-electrode cell was used for electrochemical measurements. HC-2000 composite electrode, natural graphite composite electrode, and sodium metal were used as the working electrode, counter electrode, and reference electrode, respectively. The electrolytes were prepared using sodium bis(trifluoromethanesulfonyl) amide (NaTFSA), sodium bis(fluorosulfonyl) amide (NaFSA), and NaPF6 as sodium salts and ethylene carbonate (EC) + diethyl carbonate (DEC) (1:1 by volume) and fluoroethylene carbonate (FEC) as solvents.Cyclic voltammetry (CV) was performed to form SEI on HC-2000. The scan rate and range were 0.1 mV s−1 and 0–2.5 V, respectively. After CV, electrochemical impedance spectroscopy (EIS) was performed with an electrode potential of 0.2 V and an AC amplitude of 10 mV in the frequency range of 100 kHz–10 mHz. In addition, X-ray photoelectron spectroscopy (XPS) was used to analyze the electrode after CV measurements with respect to SEI. Results and discussion Figure 1 shows the Nyquist plots obtained from the EIS analyses. The semicircles in the low frequency region were attributed to the charge-transfer resistances. Among EC+DEC solvents, the system of NaFSA had the largest charge-transfer resistance. For NaTFSA and NaPF6, the charge-transfer resistances increased in the FEC solvent, while no significant differences in the charge-transfer resistance were observed for the NaFSA system in the EC+DEC and FEC solvents.The SEI components of the HC-2000 composite electrode in each electrolyte were determined by XPS analysis after CV measurements. In NaFSA/EC+DEC system, the amount of NaF was remarkably large, while the amount of NaF was relatively small in NaTFSA/EC+DEC and NaPF6/EC+DEC systems. On the other hand, in FEC solvents, the amount of NaF increased in NaTFSA and NaPF6 systems. The systems with higher NaF contents had the larger charge-transfer resistances. This result indicates that NaF was involved in the charge-transfer resistance.Finally, EIS analyses were performed at different temperatures. The activation energies were calculated using Arrhenius plots and the Arrhenius equation. The values of the activation energies were in the range of 60–70 kJ mol−1. There was a slight variation in the values, but they were within the error range and were not significantly different for all systems. These results showed that NaF affects the frequency factor rather than the activation energy. Conclusion The effects of SEI on the interfacial reaction between electrolyte and non-graphitizable carbon were investigated. The systems with the large charge-transfer resistance had a large amount of NaF. NaF did not affect the activation energy of charge-transfer resistance but did affect the frequency factor.