Homogeneous Solid Electrolyte Interphase Research Articles

Electrolyte Design for NMC811||SiOx-Gr Lithium-Ion Batteries with Excellent Low-Temperature and High-Rate Performance

Abstract The use of high-nickel NMC811 cathode and SiOx-Gr anode can greatly improve the overall energy densities of lithium-ion batteries. However, the unfavorable solid electrolyte interphase (SEI) layer generated from the decomposition of EC-based electrolytes lead to the poor cycling stability of NMC811||SiOx-Gr cells. Here we report an electrolyte design of 1.5 M LiPF6 dissolved in FEC/MA/BN 2:2:6 by volume, which can form thin, robust, and homogeneous SEI layer to greatly improve the charge transfer at the electrode-electrolyte interface. Importantly, the designed electrolyte shows an outstanding low temperature performance that it can deliver a capacity of 123.3 mAh g–1 after 50 cycles at -20℃ with a current density of 0.5 C, overwhelming the standard EC-based electrolyte (1.2 M LiPF6 EC/EMC 3:7 by volume) with a capacity of 35.7 mAh g–1. The electrolyte also has a superior rate performance that it achieves a capacity of 122.5 mAh g-1 at a high current density of 10 C. Moreover, the LTE electrolyte holds the great potential of extreme fast-charging ability because of the large part of CC contribution in the CCCV charging model at high charging current densities.

Binary Cation Matrix Electrolyte and Its Effect on Solid Electrolyte Interphase Suppression and Evolution of Si Anode.

An unstable solid electrolyte interphase (SEI) has been recognized as one of the biggest challenges to commercializing silicon (Si) anodes for high-energy-density batteries. This work thoroughly investigates a binary cation matrix of Mg2++Li+ electrolyte and its role in SEI development, suppression, and evolution of a Si anode. Findings demonstrate that introducing Mg ions dramatically reduces the SEI growth before lithiation occurs, primarily due to the suppression of solvent reduction, particularly ethylene carbonate (EC) reduction. The Mg2+ alters the Li+ cation solvation environment as EC preferably participates in the oxophyllic Mg2+ solvation sheath, thereby altering the solvent reduction process, resulting in a distinct SEI formation mechanism. The initial SEI formation before lithiation is reduced by 70% in the electrolyte with the presence of Mg2+ cations. While the SEI continues to develop in the postlithiation, the inclusion of Mg ions results in an approximately 80% reduction in the postlithiation SEI growth. Continuous electrochemical cycling reveals that Mg2+ plays a crucial role in stabilizing the deep-lithiated Si phases, which effectively mitigates side reactions, resulting in controlled SEI growth and stable interphase while eliminating complex LixSiy formation. Mg ions promote the development of a notably more rigid and homogeneous SEI, characterized by a reduced dissipation (ΔD) in the Mg2++Li+ ion matrix compared to the solely Li+ system. This report reveals how the Mg2++Li+ ion matrix affects the SEI evolution, viscoelastic properties, and electrochemical behavior at the Si interface in real time, laying the groundwork for devising strategies to enhance the performance and longevity of Si-based next-generation battery systems.

Facile preparation of surface-modified polypropylene nanofiber separators with enhanced ionic transport and welding performance for lithium-ion batteries

Nanofiber separators are promising for high-performance lithium-ion batteries due to their high porosity and electrolyte uptake. However, most of them have been criticized for the low mechanical strength, particularly polyolefin nanofiber separators, due to the poor welding performance caused by weak interaction among the fibers. The lack of mass-production techniques is another problem for polyolefin nanofiber separators though polyolefin has the competitive cost and stability. In present study, polypropylene nanofiber separators (PPNFS) prepared via nanolayer coextrusion, a new appeared method suitable for large-scale preparation, are surface modified via a simple dip-coating method. The electrostatic self-assembly on the surface of polypropylene nanofibers is achieved. The incorporation of modified polymers significantly enhances the interaction at the nanofiber overlaps, facilitating in-situ welding of nanofibers and resulting in an 800 % enhancement in separator mechanical properties. Polybenzimidazole (PBI) is a strange polymer with both electron-donating and electron-accepting sites. Experimental characterization and simulation calculations confirm that PBI-modified PPNFS exhibit a distinctive enhanced ionic transport and promote the formation of a more homogeneous solid electrolyte interphase (SEI) layer. Furthermore, PBI coated PPNFS (PPNFS@PBI) separators demonstrate exceptional thermal stability, superior electrolyte uptake, and enhanced fire resistance. Finally, the effect of molar concentration and molecular weight of PBI on battery performance is evaluated. 15 % Molar concentration of PBI with 88,000 molecular weight has been shown to maximize battery performance.

Lignin‐derived hard carbon anode with a robust solid electrolyte interphase for boosted sodium storage performance

AbstractHard carbon is regarded as a promising anode candidate for sodium‐ion batteries due to its low cost, relatively low working voltage, and satisfactory specific capacity. However, it still remains a challenge to obtain a high‐performance hard carbon anode from cost‐effective carbon sources. In addition, the solid electrolyte interphase (SEI) is subjected to continuous rupture during battery cycling, leading to fast capacity decay. Herein, a lignin‐based hard carbon with robust SEI is developed to address these issues, effectively killing two birds with one stone. An innovative gas‐phase removal‐assisted aqueous washing strategy is developed to remove excessive sodium in the precursor to upcycle industrial lignin into high‐value hard carbon, which demonstrated an ultrahigh sodium storage capacity of 359 mAh g−1. It is found that the residual sodium components from lignin on hard carbon act as active sites that controllably regulate the composition and morphology of SEI and guide homogeneous SEI growth by a near‐shore aggregation mechanism to form thin, dense, and organic‐rich SEI. Benefiting from these merits, the as‐developed SEI shows fast Na+ transfer at the interphases and enhanced structural stability, thus preventing SEI rupture and reformation, and ultimately leading to a comprehensive improvement in sodium storage performance.

Refining the inner Helmholtz plane adsorption for achieving a stable solid-electrolyte interphase in reversible aqueous Zn-ion pouch cells

The reversibility and stability of aqueous Zn ion batteries (AZIBs) is extremely dependent on inner Helmholtz plane (IHP) structure and properties at the zinc anode/aqueous electrolyte interface. The hydrogen evolution reaction, corrosion, passivation, and uncontrolled growth of Zn dendrites all stem from the abundant presence of active H2O and irregular deposition of Zn within the IHP. In this study, we propose a strategy by using N, N'-Methylenebisacrylamide (MBA) as a bis-zincophilic site additive to effectively regulate molecular distribution within the IHP. This approach can prevent active H2O molecules from decomposing and suppress side reactions, while also can homogenize ion flux to obtain the uniform Zn deposition and stripping. Moreover, the adsorption of MBA onto IHP promotes the formation of a compact and homogeneous solid-electrolyte interphase (SEI). As a result, the utilization of an MBA/ZnSO4 electrolyte resulted in exceptional Coulombic efficiency of 99.7 % for up to 1300 cycles. The Zn//Zn symmetric pouch cell demonstrated an impressively high accumulated capacity exceeding 15,000 mA h. Furthermore, the Zn//NH4V4O10 zinc-ion pouch cell exhibited a capacity retention rate of 85 % after undergoing 1000 cycles at a current density of 1 A g−1. These results highlight the significant potential of incorporating MBA additive into practical applications.

An MPM-Based Phase-Field Simulation of Plating and Stripping of Lithium with a Solid Electrolyte Interphase

A methodology for performing phase-field simulations of plating and stripping in the presence of a solid electrolyte interphase (SEI) is presented and applied to a lithium metal electrode. Material point method (MPM) simulations are performed assuming a homogeneous SEI layer and are compared with experiment. Results are consistent with experiment for two electrolytes and confirm the dominance of the SEI layer in determining cell impedance. Notably, in some instances, the SEI potential drop greatly affected activation overpotential, differing from the applied potential. To accurately depict stripping current vs potential for SEI-free systems, the model considered non-ideal electrolyte effects: concentration-dependent salt activity coefficient, salt diffusion coefficient, and electrolyte conductivity. Conversely, systems with SEI layers displayed minimal non-ideal concentration-related electrolyte effects due to impedance originating primarily from the SEI. In plating scenarios, low SEI salt concentration negated the need for non-ideal SEI effects. However, for stripping, non-ideal salt-concentration dependent SEI effects were crucial in reproducing experimental behavior, owing to high salt concentration at the electrode/SEI interface.

Origin of Heterogeneous Stripping of Lithium in Liquid Electrolytes.

Lithium metal batteries suffer from low cycle life. During discharge, parts of the lithium are not stripped reversibly and remain isolated from the current collector. This isolated lithium is trapped in the insulating remaining solid-electrolyte interphase (SEI) shell and contributes to the capacity loss. However, a fundamental understanding of why isolated lithium forms and how it can be mitigated is lacking. In this article, we perform a combined theoretical and experimental study to understand isolated lithium formation during stripping. We derive a thermodynamic consistent model of lithium dissolution and find that the interaction between lithium and SEI leads to locally preferred stripping and isolated lithium formation. Based on a cryogenic transmission electron microscopy (cryo TEM) setup, we reveal that these local effects are particularly pronounced at kinks of lithium whiskers. We find that lithium stripping can be heterogeneous both on a nanoscale and on a larger scale. Cryo TEM observations confirm our theoretical prediction that isolated lithium occurs less at higher stripping current densities. The origin of isolated lithium lies in local effects, such as heterogeneous SEI, stress fields, or the geometric shape of the deposits. We conclude that in order to mitigate isolated lithium, a uniform lithium morphology during plating and a homogeneous SEI are indispensable.

Solid-Electrolyte Interphase Formation in Amide-Type Ionic Liquids in the Presence of Different Metal Cations

The formation of solid-electrolyte interphase (SEI) on a glassy carbon (GC) electrode in 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide (BMPFSA) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA) containing Li+, Na+, K+, and Ni2+ was investigated using the redox reaction of ferrocene (Fc). The anodic peak potential (E pa) for the oxidation of Fc changed after holding the electrode at –1.4 to –1.5 V vs Ag|Ag(I) in BMPFSA in the presence of the alkali metal ions. The decomposition of FSA– was confirmed by X-ray photoelectron spectroscopy (XPS) on a GC electrode held at –1.5 V vs Ag|Ag(I) for 6 h in BMPFSA containing the alkali metal ions. The change in E pa may also suggest the formation of homogeneous SEI in the FSA–-type ionic liquid. Moreover, E pa changed after holding the electrode at the potential more negative than –0.9 V vs Ag|Ag(I) in 50 mM Ni(TFSA)2/BMPTFSA while the decomposition of TFSA– was not confirmed by XPS on the electrode held at –1.1 V vs Ag|Ag(I) for 6 h, suggesting the bonds except C-F (e.g., S-C) were dissociated to form the SEI. Since the deposition potential of Ni in BMPTFSA was more negative than the SEI formation potential, the deposition of Ni may be inhibited by the SEI.

Deciphering the Dynamic Processes at the Electrode-Electrolyte Interface for Stable Deposition of Lithium.

Realization of lithium-metal (Li) batteries is plagued by the dendritic deposition of Li leading to internal short-circuit and low Coulombic efficiency. The Li-deposition process largely depends on the liquid electrolyte that reacts with the Li metal and forms a solid electrolyte interphase (SEI) layer with diverse chemical and physical properties. Moreover, the electrolyte possesses characteristic ion transport behaviors and directly affects the deposition kinetics at the electrode surface. As a result, the convolution of interfacial, ion transport, and kinetic effects of an electrolyte obscures the understanding of Li deposition in Li-metal batteries. Herein, the dynamic processes and the interfacial properties of Li-metal electrodes are precisely delineated in representative ether electrolytes. It is found that a combination of homogeneous SEI and slow deposition kinetics produces layer-by-layer epitaxial growth of Li. In contrast, the dendritic growth of Li is observed when the SEI is inhomogeneous and the reaction rate is fast. Nevertheless, it is shown that a homogeneous SEI is not a prerequisite in suppressing Li dendrites when the adverse effect of an unfavorable SEI can be subdued by proper kinetic tuning at the interface. Furthermore, an otherwise kinetically unstable electrolyte can also be made compatible with the Li-metal electrode when covered with a properly designed SEI. This delineation of the roles of SEI and deposition kinetics gives deep insight into designing efficient electrolytes in Li-metal batteries.

Long-Life Lithium-Metal All-Solid-State Batteries and Stable Li Plating Enabled by InSitu Formation of Li3 PS4 in the SEI Layer.

An ultrastable and kinetically favorable interface is constructed between sulfide-poly(ethylene oxide) (PEO) composite solid electrolytes (CSEs) and lithium metal, via insitu formation of a solid electrolyte interphase (SEI) layer containing Li3 PS4 . A speciallydesigned sulfide, lithium polysulfidophosphate (LPS), can distribute uniformly in the PEO matrix via a simple stirring process because of its complete solubility in acetonitrile solvent, which is advantageous for creating a homogeneous SEI layer. The CSE/Li interface with high Li+ transportation capability is stabilized quickly through insitu formation of a Li3 PS4 /Li2 S/LiF layer via the reaction between LPS and lithium metal to inhibit lithium dendrite growth. A Li/Li symmetric cell with the LPS-integrated CSE exhibits constant and small CSE/Li resistance of 10Ωcm2 during cycling, delivering stable cycling for 3475h at a current density of 0.2mAcm-2 and a high critical current density of 0.9mAcm-2 at 60°C. Impressive electrochemical performance is also demonstrated for LiFePO4 /CSE/Li all-solid-state batteries with capacity of 127.6mAhg-1 after 1000cycles at 1C.

Regulating lithium-ion flux in the solid electrolyte interphase layer to prevent lithium dendrite growth on lithium metal anode

High theoretical capacity and lowest electrochemical potential make lithium metal anode the most suitable anode material for lithium-ion batteries (LIBs). However, Lithium dendrite growth on lithium metal anode hinders proper discharge capacity and practical cycle life of LIBs. It dues to high lithium-ion flux in the solid electrolyte interphase (SEI) layer versus low diffusion in anode structure. Herein, we employ argon and oxygen plasma to modify commercial polypropylene separator surface to negatively functionalize the separator surface and discuss the influence of increasing surface negative charge on lithium dendrite growth and formation of SEI layer. Comparing electrochemical and battery performance of unmodified and plasma modified separators demonstrates, increased negative surface charge prevents lithium dendrite growth and makes a uniform and thin SEI layer due to lowering lithium-ion flux in the SEI layer. More precisely, we conduct that coulombic interaction between plasma modified separator's surface and electrolyte's cations (anions) can regulate lithium-ion flux in the SEI layer, preventing lithium dendrite growth and making thin homogeneous SEI layer on lithium metal anode structure.

An electron-deficient carbon current collector for anode-free Li-metal batteries

The long-term cycling of anode-free Li-metal cells (i.e., cells where the negative electrode is in situ formed by electrodeposition on an electronically conductive matrix of lithium sourced from the positive electrode) using a liquid electrolyte is affected by the formation of an inhomogeneous solid electrolyte interphase (SEI) on the current collector and irregular Li deposition. To circumvent these issues, we report an atomically defective carbon current collector where multivacancy defects induce homogeneous SEI formation on the current collector and uniform Li nucleation and growth to obtain a dense Li morphology. Via simulations and experimental measurements and analyses, we demonstrate the beneficial effect of electron deficiency on the Li hosting behavior of the carbon current collector. Furthermore, we report the results of testing anode-free coin cells comprising a multivacancy defective carbon current collector, a LixNi0.8Co0.1Mn0.1-based cathode and a nonaqueous Li-containing electrolyte solution. These cells retain 90% of their initial capacity for over 50 cycles under lean electrolyte conditions.

High-Safety and High-Voltage Lithium Metal Batteries Enabled by a Nonflammable Ether-Based Electrolyte with Phosphazene as a Cosolvent.

The high reactivity between lithium metal and traditional carbonate electrolytes is a great obstacle to realize the long-term cycling ability of lithium metal batteries. Ether-based electrolytes have good stability toward lithium metal anodes. However, the oxidation stability of ether-based electrolytes is generally lower than 4 V, which limits the application of high-voltage (>4 V) cathodes and restricts the energy density. The high flammability of ether is another key issue that hinders the commercialization of ether-based electrolytes. To address these issues, herein, we report a high-voltage, nonflammable ether-based electrolyte with F-, N-, and P-rich hexafluorocyclotriphosphazene (HFPN) as a cosolvent. HFPN can not only act as a highly efficient flame-retarding agent but also form a dense and homogeneous solid electrolyte interphase (SEI) layer rich in LiF and Li3N on the lithium metal anode, which stabilizes the lithium/electrolyte interface and inhibits the formation of lithium dendrites. Moreover, the HFPN-based electrolyte has a wider potential window than 4 V. As a result, with this electrolyte, high-voltage lithium metal batteries exhibit a capacity retention of ∼95% after 100 cycles. This study may provide a new pathway for developing safe, high-energy, and dendrite-free lithium metal batteries.

Micromechanism in All-Solid-State Alloy-Metal Batteries: Regulating Homogeneous Lithium Precipitation and Flexible Solid Electrolyte Interphase Evolution.

Sulfide-based solid-state electrolytes (SSEs) matched with alloy anodes are considered as promising candidates for application in all-solid-state batteries (ASSBs) to overcome the bottlenecks of the lithium (Li) anode. However, an understanding of the dynamic electrochemical processes on alloy anode in SSE is still elusive. Herein, in situ atomic force microscopy gives insights into the block-formation and stack-accumulation behaviors of Li precipitation on an Li electrode, uncovering the morphological evolution of nanoscale Li deposition/dissolution in ASSBs. Furthermore, two-dimensional Li-indium (In) alloy lamellae and the homogeneous solid electrolyte interphase (SEI) shell on the In electrode reveal the precipitation mechanism microscopically regulated by the alloy anode. The flexible and wrinkle-structure SEI shell further enables the electrode protection and inner Li accommodation upon cycles, elucidating the functional influences of SEI shell on the cycling behaviors. Such on-site tracking of the morphological evolution and dynamic mechanism provide an in-depth understanding and thus benefit the optimizations of alloy-based ASSBs.

Effects of Atmospheric Gases on Li Metal Cyclability and Solid-Electrolyte Interphase Formation.

For Li–air batteries, dissolved gas can cross over from the air electrode to the Li metal anode and affect the solid-electrolyte interphase (SEI) formation, a phenomenon that has not been fully characterized. In this work, the impact of atmospheric gases on the SEI properties is studied using electrochemical methods and ex situ characterization techniques, including X-ray photoelectron spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The presence of O2 significantly improved the lithium cyclability; less lithium is consumed to form the SEI or is lost because of electrical disconnects. However, the SEI resistivity and plating overpotentials increased. Lithium cycled in an “air-like” mixed O2/N2 environment also demonstrated improved cycling efficiency, suggesting that dissolved O2 participates in electrolyte reduction, forming a homogeneous SEI, even at low concentrations. The impact of gas environments on Li metal plating and SEI formation represents an additional parameter in designing future Li-metal batteries.

Simple and Effective Gas-Phase Doping for Lithium Metal Protection in Lithium Metal Batteries

Increasing demands for advanced lithium batteries with higher energy density have resurrected the use of lithium metal as an anode, whose practical implementation has still been restricted, because of its intrinsic problems originating from the high reactivity of elemental lithium metal. Herein, we explore a facile strategy of doping gas phase into electrolyte to stabilize lithium metal and suppress the selective lithium growth through the formation of stable and homogeneous solid electrolyte interphase (SEI) layer. We find that the sulfur dioxide gas additive doped in electrolyte significantly improves both chemical and electrochemical stability of lithium metal electrodes. It is demonstrated that the cycle stability of the lithium cells can be remarkably prolonged, because of the compact and homogeneous SEI layers consisting of Li–S–O reduction products formed on the lithium metal surface. Simulations on the lithium metal growth process suggested the homogeneity of the protective layer induced by the ga...

Quantification of the Mass and Viscoelasticity of Interfacial Films on Tin Anodes Using EQCM-D.

Electrochemical quartz crystal microbalance coupled with dissipation (EQCM-D) is employed to investigate the solid electrolyte interphase (SEI) formation and Li insertion/deinsertion into thin film electrodes of tin. Based on the frequency change we find that the initial SEI formation process is rapid before Li insertion but varies significantly with increasing concentration of the additive fluoroethylene carbonate (FEC) in the electrolyte. The extent of dissipation, which represents the film rigidity, increases with cycle number, reflecting film thickening and softening. Dissipation values are almost twice as large in the baseline electrolyte (1.2 M LiPF6 in 3:7 wt % ethylene carbonate:ethyl methyl carbonate), indicating the film in baseline electrolyte is roughly twice as soft as in the FEC-containing cells. More importantly, we detail how quantitative data about mass, thickness, shear elastic modulus, and shear viscosity in a time-resolved manner can be obtained from the EQCM-D response. These parameters were extracted from the frequency and dissipation results at multiple harmonics using the Sauerbrey and Voigt viscoelastic models. From these modeled results we show the dynamic mass changes for each half cycle. We also demonstrate that different amounts of FEC additive influence the SEI formation behavior and result in differences in the estimated mass, shear modulus and viscosity. After three cycles, the film in baseline electrolyte exhibits a 1.2 times larger mass change compared with the film in the FEC-containing electrolyte. The shear elastic modulus of films formed in the presence of FEC is larger than in the baseline electrolyte at early stages of lithiation. Also with lithiation is a marked increase in film viscosity, which together point to a much stiffer and more homogeneous SEI formed in the presence of FEC.

In-operando evaluation of the effect of vinylene carbonate on the insulating character of the solid electrolyte interphase

The solid electrolyte interphase (SEI) is an electronic insulating layer which highly affects the performance of lithium-ion batteries, especially when electrodes with low (de-)intercalation potentials such as graphite are employed. The formation of the SEI was investigated in-operando on graphite when vinylene carbonate (VC) was present as an additive in solution using feedback-mode SECM. The potential at which the surface started to become insulating was at 0.8 V vs. Li/Li+ in VC-free electrolytes, while it was at 1.3 V in VC-containing electrolytes. Nevertheless, potentials more cathodic than 0.8 V have to be reached to form a homogeneous SEI. No influence in the electronic properties of the formed SEI with different concentrations of VC was observed.