The Regulation of Solid Electrolyte Interphase on Composite Lithium Anodes in Solid-State Batteries.

Solid-state lithium metal batteries (SSLMBs) with solid polymer electrolyte (SPE) are highly promising for next-generation energy storage due to their enhanced safety and energy density. However, the stability of the solid electrolyte interphase (SEI) on the lithium metal/SPE interface is a major challenge, as continuous SEI degradation and regeneration during cycling lead to capacity fading. This article investigates the SEI formation on lithium anodes (l-SEI) and composite lithium anodes (c-SEI) in solid-state lithium metal batteries. The composite anodes form a uniform Li2S-rich inorganic SEI layer and a thinner organic SEI layer, effectively passivating the interface for enhanced cycling stability. Specifically, the full cells with c-SEI anodes sustain over 400 cycles at 0.5 C under a high areal capacity of 2.0 mAh cm-2. Moreover, the reversible high-loading solid-state pouch cells exhibit exceptional safety even after curling and cutting. These findings offer valuable insights into developing composite electrodes with robust SEI for solid-state polymer-based lithium metal batteries.

Facile Electrodeposition Method for Constructing Li2S as Artificial Solid Electrolyte Interphase for High-Performance Li Metal Anode.

Designing current collectors and constructing efficient artificial solid electrolyte interphase (SEI) layers are promising strategies for achieving dendrite-free Li deposition and practical applications in Li metal batteries (LMBs). Electrodeposition is advantageous for large-scale production and allows the direct formation of current collectors without binders, making them immediately usable as electrodes. In this study, an adherent Cu2S thin-layer on Cu foil is synthesized through anodic electrodeposition from a Na2S solution in a one-step process, followed by the generation of Li2S layers as artificial SEI layers via a conversion reaction (3DLi2S-Cu foil). The Li2S layers move from the 3D Cu surface to the deposited Li surface, facilitating uniform and dense Li deposition. The 3DLi2S-Cu foil structure demonstrates stable cycling performance over 350 cycles in an asymmetric cell, with a capacity of 1 mAh cm-2 at 1 mA cm-2. Moreover, symmetric cells with 5 mAh cm-2 of deposited Li exhibit a stable cycle life for over 1200 h. When paired with commercial LiFePO4 (LFP), the full cells show substantially enhanced cyclability, regardless of the amount of deposited Li. This study provides new insights into the construction of artificial SEIs for facilitating commercial applications.

A CaI2-Based Electrolyte Enabled by Borate Ester Anion Receptors for Reversible Ca-Organic and Ca-Se Batteries.

Passivating solid electrolyte interphases (SEIs) in Ca metal anodes constitute a long-standing challenge, as they block Ca2+ transport and inhibit reversible Ca deposition/stripping. Current solutions focus primarily on boron/aluminum-based electrolytes to mitigate such interfacial issues by producing Ca2+-conductive species, yet the complex synthetic procedure of these salts restricts the widespread application. Moreover, whether any inorganic phases possess decent Ca2+ conductivity within SEIs remains ambiguous. Herein, we report that a commercially available CaI2-dimethoxyethane electrolyte supports reversible Ca/Ca2+ redox reactions via forming CaI2-involved SEI, inspired by our density functional theory calculations where CaI2 species is predicted to possess the lowest Ca2+ diffusion barrier among a range of inorganic phases. We further materialize this finding by introducing a serial of borate ester anion receptors, resulting in the formation of CaI2/borides hybrid SEIs with an enhanced Ca2+ conductivity. Consequently, the resultant electrolytes realize a 7-fold reduction in deposition/stripping overpotential compared to anion receptor-free one, allowing for the construction of reversible Ca-metal full cells with high-capacity selenium and organic cathodes.

Vertically Fluorinated Graphene Encapsulated SiOx Anode for Enhanced Li+ Transport and Interfacial Stability in High-Energy-Density Lithium Batteries.

Achieving high energy density has always been the goal of lithium-ion batteries (LIBs). SiOx has emerged as a compelling candidate for use as a negative electrode material due to its remarkable capacity. However, the huge volume expansion and the unstable electrode interface during (de)lithiation, hinder its further development. Herein, we report a facile strategy for the synthesis of surface fluorinated SiOx (SiOx@vG-F), and investigate their influences on battery performance. Systematic experiments investigations indicate that the reaction between Li+ and fluorine groups promotes the in situ formation of stable LiF-rich solid electrolyte interface (SEI) on the surface of SiOx@vG-F anode, which effectively suppresses the pulverization of microsized SiOx particles during the charge and discharge cycle. As a result, the SiOx@vG-F enabled a higher capacity retention of 86.4 % over 200 cycles at 1.0 C in the SiOx@vG-F||LiNi0.8Co0.1Mn0.1O2 full cell. This approach will provide insights for the advancement of alternative electrode materials in diverse energy conversion and storage systems.

Insight into Fluoride Additives to Enhance Ammonia Production from Lithium-Mediated Electrochemical Nitrogen Reduction Reaction.

Demands for green ammonia production increase due to its application as a proton carrier, and recent achievements in electrochemical Li-mediated nitrogen reduction reactions (Li-NRRs) show promising reliability. Here, it is demonstrated that F-containing additives in the electrolyte improve ammonia production by modulating the solid electrolyte interphase (SEI). It is suggested that the anionic additives with low lowest unoccupied molecular orbital levels enhance efficiency by contributing to the formation of a conductive SEI incorporated with LiF. Specifically, as little as 0.3 wt.% of BF4 - additive to the electrolyte, the Faradaic efficiency (FE) for ammonia production is enhanced by over 15% compared to an additive-free electrolyte, achieving a high yield of 161 ± 3 nmol s-1 cm-2. The BF4 - additive exhibits advantages, with decreased overpotential and improved FE, compared to its use as the bulk electrolyte. The observation of the Li3N upper layer implies that active Li-NRR catalytic cycles are occurring on the outermost SEI, and density functional theory simulations propose that an SEI incorporated with LiF facilitates energy profiles for the protonation by adjusting the binding energies of the intermediates compared to bare copper. This study unlocks the potential of additives and offers insights into the SEIs for efficient Li-NRRs.

Covalent Organic Framework-Based Materials for Advanced Lithium Metal Batteries.

Lithium metal batteries (LMBs), with high energy densities, are strong contenders for the next generation of energy storage systems. Nevertheless, the unregulated growth of lithium dendrites and the unstable solid electrolyte interphase (SEI) significantly hamper their cycling efficiency and raise serious safety concerns, rendering LMBs unfeasible for real-world implementation. Covalent organic frameworks (COFs) and their derivatives have emerged as multifunctional materials with significant potential for addressing the inherent problems of the anode electrode of the lithium metal. This potential stems from their abundant metal-affine functional groups, internal channels, and widely tunable architecture. The original COFs, their derivatives, and COF-based composites can effectively guide the uniform deposition of lithium ions by enhancing conductivity, transport efficiency, and mechanical strength, thereby mitigating the issue of lithium dendrite growth. This review provides a comprehensive analysis of COF-based and derived materials employed for mitigating the challenges posed by lithium dendrites in LMB. Additionally, we present prospects and recommendations for the design and engineering of materials and architectures that can render LMBs feasible for practical applications.

Towards low-temperature dendrite-free zinc anode by constructing functional MXene buffer layer with duplex zincophilic sites.

Dendrite growth and side reactions of zinc metal anode have severely limited the practical application of aqueous zinc ion batteries (AZIBs). Herein, we introduce an artificial buffer layer composed of functional MXene (Ti3CN) for zinc anodes. The synthesized Ti3CN exhibits superior conductivity and features duplex zincophilic sites (N and F). These characteristics facilitate the homogeneous deposition of Zn2+, accelerate the desolvation process of hydrated Zn2+, and reduce the nucleation overpotential. The Ti3CN-protected Zn anode demonstrates significantly enhanced reversibility compared to bare Zn anode during long-term cycling, achieving a cumulative plating capacity of 10,000 mAh cm-2 at 10 mA cm-2. In Ti3CN-Zn||Cu asymmetric cell, it maintains nearly 100 % Coulombic efficiency over 2500 cycles at 2 mA cm-2. Furthermore, the assembled Ti3CN-Zn//δ-K0.51V2O5 (KVO) full cell exhibit a low capacity decay rate of 0.002 % per cycle at 5 A/g. Even at 0 °C, the Ti3CN-Zn symmetric cell maintains steady cycling for 2000 h. This study introduces a novel approach for designing artificial solid electrolyte interlayers for commercial AZIBs.

Reduction-Tolerance Electrolyte Design for High-Energy Lithium Batteries.

Lithium batteries employing Li or silicon (Si) anodes hold promise for the next-generation energy storage systems. However, their cycling behavior encounters rapid capacity degradation due to the vulnerability of solid electrolyte interphases (SEIs). Though anion-derived SEIs mitigate this degradation, the unavoidable reduction of solvents introduces heterogeneity to SEIs, leading to fractures during cycling. Here, we elucidate how the reductive stability of solvents, dominated by the electrophilicity (EPT) and coordination ability (CDA), delineates the SEI formed on Li or Si anodes. Solvents exhibiting lower EPT and CDA demonstrate enhanced tolerance to reduction, resulting in inorganic-rich SEIs with homogeneity. Guided by these criteria, we synthesized three promising solvents tailored for Li or Si anodes. The decomposition of these solvents is dictated by their EPTs under similar solvation structures, imparting distinct characteristics to SEIs and impacting battery performance. The optimized electrolyte, 1 M lithium bis(fluorosulfonyl)imide (LiFSI) in N-Pyrrolidine-trifluoromethanesulfonamide (TFSPY), achieves 600 cycles of Si anodes with a capacity retention of 81 % (1910 mAh g-1). In anode-free Cu||LiNi0.5Co0.2Mn0.3O2 (NCM523) pouch cells, this electrolyte sustains over 100 cycles with an 82 % capacity retention. These findings illustrate that reducing solvent decomposition benefits SEI formation, offering valuable insights for the designing electrolytes in high-energy lithium batteries.

A Fluoride-Rich Solid-Like Electrolyte Stabilizing Lithium Metal Batteries.

To address the problems associated with Li metal anodes, a fluoride-rich solid-like electrolyte (SLE) that combines the benefits of solid-state and liquid electrolytes is presented. Its unique triflate-group-enhanced frame channels facilitate the formation of a functional inorganic-rich solid electrolyte interphase (SEI), which not only improves the reversibility and interfacial charge transfer of Li anodes but also ensures uniform and compact Li deposition. Furthermore, these triflate groups contribute to the decoupling of Li+ and provide hopping sites for rapid Li+ transport, enabling a high room-temperature ionic conductivity of 1.1 mS cm-1 and a low activation energy of 0.17 eV, making it comparable to conventional liquid electrolytes. Consequently, Li symmetric cells using such SLE achieve extremely stable plating/stripping cycling over 3500 h at 0.5 mA cm-2 and support a high critical current up to 2 mA cm-2. The assembled Li||LiFePO4 solid-like batteries exhibit exceptional cyclability for over 1 year and a half, even outperforming liquid cells. Additionally, high-voltage cylindrical cells and high-capacity pouch cells are demonstrated, corroborating much simpler processibility in battery assembly compared to all-solid-state batteries.

Lithium Bis(fluorosulfonyl)imide for Stabilized Interphases on Conjugated Dicarboxylate Electrode.

Carbonyl-based negative electrodes have received considerable interest in the domain of rechargeable lithium batteries, owing to their superior feasibility in structural design, enhanced energy density, and good environmental sustainability. Among which, lithium terephthalate (LiTPA) has been intensively investigated as a negative electrode material in the past years, in light of its relatively stable discharge plateau at low potentials (ca. 1.0 V vs Li/Li+) and high specific capacity (ca. 290 mAh g-1). However, its cell performances are severely limited owing to the poor quality of the solid-electrolyte-interphase (SEI) layer generated therein. Here, we report the utilization of lithium bis(fluorosulfonyl)imide (LiFSI) as an electrolyte salt for forming a Li-ion permeable SEI layer on the LiTPA electrode and subsequently improving the cyclability and rate performance of the LiTPA-based cells. Our results show that, differing from the reference electrolyte containing the lithium hexafluorophosphate (LiPF6) salt, the electrochemical reductions of the FSI- anions occur prior to the lithiation processes of LiTPA electrode, which is capable of building an inorganic-rich SEI layer containing lithium fluoride (LiF) and lithium sulfate (Li2SO4). Consequently, the lithium metal (Li°)||LiTPA cell shows significantly improved cycling performance than the LiPF6-based reference cell. This work provides useful insight into the reductive processes of the FSI- anions on negative electrodes, which could spur the deployment of highly sustainable and high-energy rechargeable lithium batteries.

Solvation Modulation Enhances Anion-Derived Solid Electrolyte Interphase for Deep Cycling of Aqueous Zinc Metal Batteries.

Stable Zn anodes with a high utilization efficiency pose a challenge due to notorious dendrite growth and severe side reactions. Therefore, electrolyte additives are developed to address these issues. However, the additives are always consumed by the electrochemical reactions over cycling, affecting the cycling stability. Here, hexamethylphosphoric triamide (HMPA) is reported as an electrolyte additive for achieving stable cycling of Zn anodes. HMPA reshapes the solvation structures and promotes anion decomposition, leading to the in situ formation of inorganic-rich solid-electrolyte-interphase. More interestingly, this anion decomposition does not involve HMPA, preserving its long-term impact on the electrolyte. Thus, the symmetric cells with HMPA in the electrolyte survive ≈500 h at 10 mA cm-2 for 10 mAh cm-2 or ≈200 h at 40 mA cm-2 for 10 mAh cm-2 with a Zn utilization rate of 85.6 %. The full cells of Zn||V2 O5 exhibit a record-high cumulative capacity even under a lean electrolyte condition (E/C ratio=12 µL mAh-1 ), a limited Zn supply (N/P ratio=1.8) and a high areal capacity (6.6 mAh cm-2 ).

Molecular-Cling-Effect of Fluoroethylene Carbonate Characterized via Ethoxy(pentafluoro)cyclotriphosphazene on SiOx/C Anode Materials - A New Perspective for Formerly Sub-Sufficient SEI Forming Additive Compounds.

Effective electrolyte compositions are of primary importance in raising the performance of lithium-ion batteries (LIBs). Recently, fluorinated cyclic phosphazenes in combination with fluoroethylene carbonate (FEC) have been introduced as promising electrolyte additives, which can decompose to form an effective dense, uniform, and thin protective layer on the surface of electrodes. Although the basic electrochemical aspects of cyclic fluorinated phosphazenes combined with FEC were introduced, it is still unclear how these two compounds interact constructively during operation. This study investigates the complementary effect of FEC and ethoxy(pentafluoro)cyclotriphosphazene (EtPFPN) in aprotic organic electrolyte in LiNi0.5 Co0.2 Mn0.3 O ∥ SiOx /C full cells. The formation mechanism of lithium ethyl methyl carbonate (LEMC)-EtPFPN interphasial intermediate products and the reaction mechanism of lithium alkoxide with EtPFPN are proposed and supported by Density Functional Theory calculations. A novel property of FEC is also discussed here, called molecular-cling-effect (MCE). To the best knowledge, the MCE has not been reported in the literature, although FEC belongs to one of the most investigated electrolyte additives. The beneficial MCE of FEC toward the sub-sufficient solid-electrolyte interphase forming additive compound EtPFPN is investigated via gas chromatography-mass spectrometry, gas chromatography high resolution-accurate mass spectrometry, in situ shell-isolated nanoparticle-enhanced Raman spectroscopy, and scanning electron microscopy.

Sponge-Like Porous-Conductive Polymer Coating for Ultrastable Silicon Anodes in Lithium-Ion Batteries.

Urgent calls for reversible cycling performance of silicon (Si) requires an efficient solution to maintain the silicon-electrolyte interface stable. Herein, a conductive biphenyl-polyoxadiazole (bPOD) layer is coated on Si particles to enhance the electrochemical process and prolong the cells lifespan. The conformal bPOD coatings are mixed ionicelectronic conductors, which not only inhibit the infinite growth of solid electrolyte interphase (SEI) but also endow electrodes with outstanding ion/electrons transport capacity. The superior 3D porous structure in the continuous phase allows the bPOD layers to act like a sponge to buffer volume variation, resulting in high structural stability. The in situ polymerized bPOD coating and it-driven thin LiF-rich SEI layer remarkably improve the lithium storage performance of Si anodes, showing a high reversible specific capacity of 1600 mAh g-1 even after 500 cycles at 1 A g-1 along with excellent rate capacity of over 1500 mAh g-1 at 3 A g-1 . It should be noticed that a long cycle life of 800 cycles with 1065 mAh g-1 at 3 A g-1 can also be achieved with a capacity retention of more than 80%. Therefore,  we  believe this unique polymer coating design paves the way for the widespread adoption of next-generation lithium-ion batteries.

In Situ Fabricated Non-Flammable Quasi-Solid Electrolytes for Li-Metal Batteries.

Lithium metal batteries (LMBs) are viewed as one of the most promising high energy density battery systems, but their practical application is hindered by significant fire hazards and fast performance degradation due to the lack of a safe and compatible configuration. Herein, nonflammable quasi-solid electrolytes (NQSEs) are designed and fabricated by using the in situ polymerization method, in which 1,3,2-dioxathiolan-2,2-oxide is used as both initiator to trigger the in situ polymerization of solvents and interphase formation agent to construct robust interface layers to protect the electrodes, and triethyl phosphate as a fire-retardant agent. The NQSEs show a high ionic conductivity of 0.38 mS cm-1 at room temperature and enable intimate solid-electrolyte interphases, and demonstrate excellent performance with stable plating/striping of Li metal anode, and high voltage (4.5 V) and high temperature (>60 °C) survivability. The findings provide an effective strategy to build high-temperature, high-energy density, and safe quasi-solid LMBs.

Correlating Solid Electrolyte Interphase Composition with Dendrite-Free and Long Life-Span Lithium Metal Batteries via Advanced Characterizations and Simulations.

Lithium metal anode attracts great attention because of its high specific capacity and low redox potential. However, the uncontrolled dendrite growth and its infinite volume expansion during cycling are extremely detrimental to the practical application. The formation of a solid electrolyte interphase (SEI) plays a decisive role in the behavior of lithium deposition/dissolution during electrochemical processing. Clarifying the essential relationship between SEI and battery performance is a priority. Research in SEI is accelerated in recent years by the use of advanced simulation tools and characterization techniques. The chemical composition and micromorphology of SEIs with various electrolytes are analyzed to clarify the effects of SEI on the Coulombic efficiency and cycle life. In this review, the recent research progress focused on the composition and structure of SEI is summarized, and various advanced characterization techniques applied to the investigation of SEI are discussed. The comparisons of the representative experimental results and theoretical models of SEI in lithium metal batteries (LMBs) are exhibited, and the underneath mechanisms of interaction between SEI and the electrochemical properties of the cell are highlighted. This work offers new insights into the development of safe LMBs with higher energy density.

Electrochemistry-Driven Interphase Doubly Protects Graphite Cathodes for Ultralong Life and Fast Charge of Dual-Ion Batteries.

Dual-ion batteries (DIBs) with graphite as cathode material, show superiority in terms of sustainability, affordability, and environmental impact over Li-ion batteries that rely on transition-metal based cathodes. However, graphite cathodes severely suffer from poor structural stability during anion storage at high potentials because of the co-intercalation and oxidative decomposition of electrolytes. This work presents an in situ electrochemistry-driven route to create a bifunctional interphase through implantation of diethylenetriaminepenta(methylene-phosphonic acid) (DTPMP) on the surface of graphite particles. The reaction mechanisms and functions of DTPMP are investigated both experimentally and theoretically. The DTPMP-derived interphase not only improves the antioxidative stability of electrolytes but also benefits the desolvation of PF6 - anions, which doubly protect the graphitic structure and give rise to fast-charge and ultralong cycling performance of graphite cathodes in DIBs.

A Bifunctional Fluorine-Free Electrolyte Additive for Realizing Dendrite-Free Lithium Anodes.

Owing to the strong energy advantage of lithium anodes, the development of lithium-metal batteries has become an inevitable trend. However, plagued by the instability of solid-electrolyte interphase (SEI) films, lithium metal anodes face challenges such as lithium dendrite formation and volume expansion. Studies have proven that modulating the composition and structure of SEI films by using electrolyte additives is a convenient and valid method. Currently, it is widely accepted that fluoride is an effective additive but, based on the high cost of fluoride production and environmental concerns, the development of fluoride-free additives is of great significance. In this work, the bifunctional additive N,O-bis(trimethylsilyl)acetamide (BSA) is proposed, which can build up a SEI layer that is rich in SiOx and Li3 N on the surface of the lithium anode to control the deposition behavior of lithium and clean the electrolyte of HF to protect the electrode. The experimental results indicate that BSA suppresses the generation of lithium dendrites and controls the volume expansion of lithium anodes. Moreover, compared with the commonly used carbonate electrolytes, the battery containing BSA has the best overall performance. Methodologically, the results can be extended to other additives containing Si-O functional groups to replace the same type of fluorine-containing additives.

Accessing the Primary Solid-Electrolyte Interphase on Lithium Metal: A Method for Low-Concentration Compound Analysis.

Despite large research efforts in the fields of lithium ion and lithium metal batteries, there are still unanswered questions. One of them is the formation of the solid-electrolyte interphase (SEI) in lithium-metal-anode-based battery systems. Until now, a compound profile analysis of the SEI on lithium metal was challenging as the amounts of many compounds after simple contact of lithium metal and the electrolyte were too low for detection with analytical methods. This study presents a novel approach on unravelling the SEI compound profile through accumulation in the gas, liquid electrolyte, and solid phase. The method uses the intrinsic behavior of lithium metal to spontaneously react with the liquid electrolyte. In combination with complementary, state-of-the-art analytical instrumentation and methods, this approach provides qualitative and quantitative results on all three phases revealing the vast variety of compounds formed in carbonate-based electrolytes.

Interphase Engineering for Stabilizing Ni-Rich Cathode in Lithium-Ion Batteries by a Nucleophilic Reaction-Based Additive.

Ni-rich cathode materials are considered promising candidates for next-generation lithium-ion batteries because of their high energy density and low cost. However, interphase failure at the surface of Ni-rich cathodes negatively impacts cycling performance, making it challenging to meet the requirements of long-term applications. In this study, a strategy is developed to improve interphase properties through introduction of a nucleophilic reaction-based additive, using an appropriate amount of the inducer lithium isopropoxide (LIP) in the commercial electrolyte to achieve long-term cycling stability of Li||LiNi0.83 Co0.11 Mn0.06 O2 (NCM83) cells. This strategy enables Li||NCM83 cells to maintain a capacity of 148.7 mAh g-1 with a retention of 83.3 % even after 500 cycles. This outstanding cycling stability is attributed to a robust cathode-electrolyte interphase (CEI) constructed on NCM83 surface LIP-induce ring-opening polymerization of ethylene carbonate (EC). As a result, the organic-inorganic components of the CEI effectively constrain gas evolution and the corresponding phase transformation behavior. Furthermore, the CEI also suppresses microcrack formation and eventually sustains the Ni valence and coordination environment at high voltage.

Insights into Electrolytic Pre-Lithiation: A Thorough Analysis Using Silicon Thin Film Anodes.

Pre-lithiation via electrolysis, herein defined as electrolytic pre-lithiation, using cost-efficient electrolytes based on lithium chloride (LiCl), is successfully demonstrated as a proof-of-concept for enabling lithium-ion battery full-cells with high silicon content negative electrodes. An electrolyte for pre-lithiation based on γ-butyrolactone and LiCl is optimized using boron-containing additives (lithium bis(oxalato)borate, lithium difluoro(oxalate)borate) and CO2 with respect to the formation of a protective solid electrolyte interphase (SEI) on silicon thin films as model electrodes. Reversible lithiation in Si||Li metal cells is demonstrated with Coulombic efficiencies (CEff ) of 95-96% for optimized electrolytes comparable to 1 m LiPF6 /EC:EMC 3:7. Formation of an effective SEI is shown by cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). electrolytic pre-lithiation experiments show that notable amounts of the gaseous product Cl2 dissolve in the electrolyte leading to a self-discharge Cl2 /Cl- shuttle mechanism between the electrodes lowering pre-lithiation efficiency and causing current collector corrosion. However, no significant degradation of the Si active material and the SEI due to contact with elemental chlorine is found by SEM, impedance, and XPS. In NCM111||Si full-cells, the capacity retention in the 100th cycle can be significantly increased from 54% to 78% by electrolytic pre-lithiation, compared to reference cells without pre-lithiation of Si.