Solid Electrolyte Interphase Formation Research Articles

Pyrrole as a multi-functional additive to concurrently stabilize Zn anode and cathode via interphase regulation towards advanced aqueous zinc-ion battery

The advancement of aqueous zinc-ion batteries (AZIBs) is impeded by challenges encompassing cathodic and anodic aspects, such as limited capacity and dendrite formation, constraining their broader utilization. Herein, pyrrole, an economically viable and readily accessible compound, is proposed as a versatile electrolyte additive to address these challenges. Experiments and DFT calculations reveal that pyrrole and its derivatives preferentially adsorb onto zinc foil, facilitating the formation of a pyrrole-based solid electrolyte interphase (SEI), which effectively guides uniform Zn2+ deposition through strong attraction force and suppresses hydrogen evolution reactions and parasitic reactions. On the cathode side, the additive promotes the formation of a durable cathode electrolyte interphase (CEI) enriched with poly-pyrrole (Ppy) analogues. Such layer significantly contributes to extra capacity of both polyaniline (PANI) and MnO2 cathodes by leveraging the electrochemical reactivity of Ppy towards Zn2+ and improves their cyclic stability. Consequently, a dendrite-free Zn anode is realized with an extended cyclic lifespan surpassing 6000 h in Zn//Zn cell, coupled with an average Coulombic efficiency of 99.7 % in Cu//Zn cell. Moreover, the PANI//Zn and MnO2//Zn full cells demonstrate enhanced capacities along with improved cycling stability. This work provides a new additive strategy towards concurrent stabilization of cathode and Zn anode in AZIBs.

Deciphering the degradation mechanisms of nano-Si and micro-SiO anodes in lithium-ion battery full-cells using distribution relaxation times analysis

Silicon (Si) and silicon monoxide (SiO) have attracted great interest as next-generation anode materials for lithium-ion batteries (LiBs) due to their high energy density. However, their commercialization has been hindered by rapid capacity fading, which stems from mechanical degradation (e.g., cracking and delamination) and the aggressive formation of solid electrolyte interphase (SEI) layer. While understanding these degradation mechanisms in batteries necessitates in-operando measurement techniques, very few non-destructive analytical methods have been documented in literature. This paper highlights the effectiveness of combined electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) techniques in performing systematic characterization of LiNi0.6Mn0.2Co0.2O2 (NMC)/nano-Si and NMC/micro-SiO full-cells. The systematic design of experiments enabled the separate deconvolution of anode and cathode aging using symmetrical cells. This approach offered a clear understanding of the overall degradation mechanisms in the full-cells. The major impedance sources in the NMC/nano-Si full-cell were anode contact impedance, resulting from mechanical degradation of Si, and cathode charge transfer impedance, due to significant lithium loss and consequently deeper extraction of lithium ions in NMC. In contrast, micro-SiO anodes exhibited less electrode-level degradation, as evidenced by SEM images and relatively stable impedance behaviors during extended cycling, which strongly corroborate its superior capacity retention (66 % at 300th cycle) compared to that of nano-Si anode in full-cells (26.5 % at 300th cycle).

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.

Evolution of Lithium Metal Anode Along Cycling in Working Lithium–Sulfur Batteries

AbstractThe cycling lifespan of high‐energy‐density lithium–sulfur (Li–S) batteries is dominantly limited by the rapid failure of Li metal anodes. Herein, the evolution of Li metal anode along cycling is systematically investigated in Li–S batteries to clarify the Li plating and stripping behaviors, the generation and accumulation of inactive Li, and the failure mechanism of Li metal anodes. Concretely, plated Li strips preferentially than bulk Li to leave massive stripping Li shells during initial discharge, and the stripping Li shells are refilled by plated Li during the subsequent charge to generate thick Li dendrites. During the following cycles, inactive Li generates and accumulates on top of bulk Li due to solid electrolyte interphase formation and incomplete removal of plated Li. Eventually, the accumulation of inactive Li hinders the diffusion of Li ions through the inactive Li layer to induce cell polarization at the end of the second discharge plateau and rapid decay of discharge capacity. This work elucidates the detailed evolution mechanism of Li metal anode along cycling in working Li–S batteries and highlights the reactivation of inactive Li as an effective strategy to prolong the cycling lifespan of Li–S batteries.

3D-Printed Hierarchically Microgrid Frameworks of Sodiophilic Co3O4@C/rGO Nanosheets for Ultralong Cyclic Sodium Metal Batteries.

Herein, hierarchically structured microgrid frameworks of Co3O4 and carbon composite deposited on reduced graphene oxide (Co3O4@C/rGO) are demonstrated through the three-dimensioinal (3D)printing method, where the porous structure is controllable and the height and width are scalable, for dendrite-free Na metal deposition. The sodiophilicity, facile Na metal deposition kinetics, and NaF-rich solid electrolyte interphase (SEI) formation of cubic Co3O4 phase are confirmed by combined spectroscopic and computational analyses. Moreover, the uniform and reversible Na plating/stripping process on 3D-printed Co3O4@C/rGO host is monitored in real time using in situ transmission electron and optical microscopies. In symmetric cells, the 3D printed Co3O4@C/rGO electrode achieves a long-term stability over 3950 at 1mA cm-2 and 1 mAh cm-2 with a superior Coulombic efficiency (CE) of 99.87% as well as 120h even at 20mA cm-2 and 20 mAh cm-2, far exceeding the previously reported carbon-based hosts for Na metal anodes. Consequently, the full cells of 3D-printed Na@Co3O4@C/rGO anode with 3D-printed Na3V2(PO4)3@C-rGO cathode (≈15.7mg cm-2) deliver the high specific capacity of 97.97 mAh g-1 after 500 cycles with a high CE of 99.89% at 0.5 C, demonstrating the real operation of flexible Na metal batteries.

Carbon cloth with lithiophilic carbon-coated ZnO nanotubes as anode current collector for hybrid lithium ion/lithium metal battery

Reasonable design of light-weight carbon-based current collector is a promising strategy to enable high-energy-density lithium batteries. Herein, carbon-coated ZnO nanotube arrays with good lithiophilicity are constructed on carbon cloth, which is used as anode current collector to construct hybrid lithium ion/lithium metal battery. The modified carbon cloth effectively promotes the formation of robust and inorganic-rich solid electrolyte interphase, which consists of mixed ionic-electronic conductive (MIEC) interface with ion-conductive Li2O/LiC6 and electron-conductive LiZn alloy. Rapid electron/ion transportation during repeated lithium plating/stripping is realized by the Li2O/LiZn/LiC6 MIEC arrays, which homogenizes the lithium deposition and ensures uniform dendrite-free Li deposition. The three-dimensional structure of the current collector also provides enough space to constrain the lithium deposition and avoid the huge volume change. As a result, continuous anode-electrolyte interfacial side reactions and active lithium loss are effectively suppressed. Uniform Li deposition and high average Coulombic efficiency are achieved in the hybrid lithium ion/lithium metal cell. The capacity retention of full cell with carbonate-based electrolyte maintains 47.0 % after 600 cycles, and the full cell also shows superiority in rate performance and energy density. This work provides a promising alternative for light-weight anode current collector to enable high-energy-density lithium batteries.

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 0.3wt.% 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 ± 3nmol 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.

Unraveling the Degradation Mechanisms of Lithium-Ion Batteries

Lithium-Ion Batteries (LIBs) usually present several degradation processes, which include their complex Solid-Electrolyte Interphase (SEI) formation process, which can result in mechanical, thermal, and chemical failures. The SEI layer is a protective layer that forms on the anode surface. The SEI layer allows the movement of lithium ions while blocking electrons, which is necessary to prevent short circuits in the battery and ensure safe operation. However, the SEI formation mechanisms reduce battery capacity and power as they consume electrolyte species, resulting in irreversible material loss. Furthermore, it is important to understand the degradation reactions of the LIBs used in Electric Vehicles (EVs), aiming to establish the battery lifespan, predict and minimise material losses, and establish an adequate time for replacement. Moreover, LIBs applied in EVs suffer from two main categories of degradation, which are, specifically, calendar degradation and cycling degradation. There are several studies about battery degradation available in the literature, including different degradation phenomena, but the degradation mechanisms of large-format LIBs have rarely been investigated. Therefore, this review aims to present a systematic review of the existing literature about LIB degradation, providing insight into the complex parameters that affect battery degradation mechanisms. Furthermore, this review has investigated the influence of time, C-rate, depth of discharge, working voltage window, thermal and mechanical stresses, and side reactions in the degradation of LIBs.

Construction of stable two-sided interface via the addition of phenylboric acid in Lithium-ion batteries

Electrolyte additive engineering is one of the most useful approaches to improve the interfacial property of electrode material in Li-ion batteries (LIBs), which plays a vital role in the mass transport during the electrochemical process. Boron-based electrolyte additives have a good application prospect, however exploring new additives with lower-cost and higher efficiency is still needed. In this study, Phenyl boric acid (PBA), acting as a two-sided interface modifier, is introduced to LiNi0.5Co0.2Mn0.3O2/SiC batteries. Through both theoretical calculations and experimental measurements, it is found that PBA could be preferentially reduced on the SiC anode and induce the formation of B-rich solid electrolyte interphase (SEI), which efficiently protects the anode material from the parasitic reaction. Besides, PBA can be sacrificially oxidized before other salt/solvent decomposition, achieving a highly-reversible lithiation/delithiation process at the cathode. Benefiting from these synergistic effects, the target Si-C/Li half-cells achieve a 2.5 % improvement in average coulomb efficiency of 100 cycles, while the capacity retention rate of NCM/Li half-cells and NCM/Si-C full cells increase by 21.4 % and 15.8 %, respectively. This work provides an effective approach to ameliorating the electrode interface chemistry of LIBs employing Si-based anodes Ni-rich cathodes and another analogous battery systems.

Rational Design of Electrolyte Additives for Improved Solid Electrolyte Interphase Formation on Graphite Anodes: A Study of 1,3,6-Hexanetrinitrile

The construction of a thin, uniform, and robust solid electrolyte interphase (SEI) film on the surface of active materials is pivotal for enhancing the overall performance of lithium-ion batteries (LiBs). However, conventional electrolytes often fail to achieve the desired SEI characteristics. In this work, we introduced 1,3,6-hexanetrinitrile (HTCN) in the baseline electrolyte (BE) of 1.0 M LiPF6 in Ethylene Carbonate/Dimethyl Carbonate (EC/DMC) (3:7 by volume) with 5 wt.% fluoroethylene carbonate (FEC), denoted as BE-FH. By systematically investigating the influence of FEC: HTCN weight ratios on the electrochemical performance of graphite anodes, we identified an optimal composition (FEC:HTCN = 5:4 by weight, denoted as BE-FH54) that demonstrated greatly improved initial Coulombic efficiency, rate capability, and cycling stability compared with the baseline electrolyte. Deviations from the optimal FEC:HTCN ratio resulted in the formation of either small cracks or excessively thick SEI layers. The enhanced performance of BE-FH54-based LiB is mainly ascribed to the synergistic effect of FEC and HTCN in forming a robust, thin, homogeneous, and ion-conducting SEI. This research highlights the importance of rational electrolyte design in enhancing the electrochemical performance of graphite anodes in LiBs and provides insights into the role of nitrile-based additives in modulating the SEI properties.

Elucidating the Transport of Electrons and Molecules in a Solid Electrolyte Interphase Close to Battery Operation Potentials Using a Four-Electrode-Based Generator-Collector Setup.

In lithium-ion batteries, the solid electrolyte interphase (SEI) passivates the anode against reductive decomposition of the electrolyte but allows for electron transfer reactions between anode and redox shuttle molecules, which are added to the electrolyte as an internal overcharge protection. In order to elucidate the origin of these poorly understood passivation properties of the SEI with regard to different molecules, we used a four-electrode-based generator-collector setup to distinguish between electrolyte reduction current and the redox molecule (ferrocenium ion Fc+) reduction current at an SEI-covered glassy carbon electrode. The experiments were carried out in situ during potentiostatic SEI formation close to battery operation potentials. The measured generator and collector currents were used to calculate passivation factors of the SEI with regard to electrolyte reduction and with regard to Fc+ reduction. These passivation factors show huge differences in their absolute values and in their temporal evolution. By making simple assumptions about molecule transport, electron transport, and charge transfer reaction rates in the SEI, distinct passivation mechanisms are identified, strong indication is found for a transition during SEI growth from redox molecule reduction at the electrode | SEI interface to reduction at the SEI | electrolyte interface, and good estimates for the transport coefficients of both electrons and redox molecules are derived. The approach presented here is applicable to any type of electrochemical interphase and should thus also be of interest for interphase characterization in the fields of electrocatalysis and corrosion.

Monitoring the Behavior of Na Ions and Solid Electrolyte Interphase Formation at an Aluminum/Ionic Liquid Electrode/Electrolyte Interface via Operando Electrochemical X-ray Photoelectron Spectroscopy.

In electrochemical energy storage devices, the interface between the electrode and the electrolyte plays a crucial role. A solid electrolyte interphase (SEI) is formed on the electrode surface due to spontaneous decomposition of the electrolyte, which in turn controls the dynamics of ion migration during charge and discharge cycles. However, the dynamic nature of the SEI means that its chemical structure evolves over time and as a function of the applied bias; thus, a true operando study is extremely valuable. X-ray photoelectron spectroscopy (XPS) is a widely used technique to understand the surface electronic and chemical properties, but the use of ultrahigh vacuum in standard instruments is a major hurdle for their utilization in measuring wet electrochemical processes. Herein, we introduce a 3-electrode electrochemical cell to probe the behavior of Na ions and the formation of SEI at the interface of an ionic liquid (IL) electrolyte and an aluminum electrode under operando conditions. A system containing 0.5 molar NaTFSI dissolved in the IL [BMIM][TFSI] was investigated using an Al working electrode and Pt counter and reference electrodes. By optimizing the scan rate of both XPS and cyclic voltammetry (CV) techniques, we captured the formation and evolution of SEI chemistry using real-time spectra acquisition techniques. A CV scan rate of 2 mVs-1 was coupled with XPS snapshot spectra collected at 10 s per core level. The technique demonstrated here provides a platform for the chemical analysis of materials beyond batteries.

Interfacial fusion-enhanced 11 µm-thick gel polymer electrolyte for high-performance lithium metal batteries

In the pursuit of ultrathin polymer electrolyte (<20 μm) for lithium metal batteries, achieving a balance between mechanical strength and interfacial stability is crucial for the longevity of the electrolytes. Herein, 11 μm-thick gel polymer electrolyte is designed via an integrated electrode/electrolyte structure supported by lithium metal anode. Benefiting from an exemplary superiority of excellent mechanical property, high ionic conductivity, and robust interfacial adhesion, the in-situ formed polymer electrolyte reinforced by titanosiloxane networks (ISPTS) embodies multifunctional roles of physical barrier, ionic carrier, and artificial protective layer at the interface. The potent interfacial interactions foster a seamless fusion of the electrode/electrolyte interfaces and enable continuous ion transport. Moreover, the built-in ISPTS electrolyte participates in the formation of gradient solid-electrolyte interphase (SEI) layer, which enhances the SEI’s structural integrity against the strain induced by volume fluctuations of lithium anode. Consequently, the resultant 11 μm-thick ISPTS electrolyte enables lithium symmetric cells with cycling stability over 600 h and LiFePO4 cells with remarkable capacity retention of 96.6% after 800 cycles. This study provides a new avenue for designing ultrathin polymer electrolytes towards stable, safe, and high-energy–density lithium metal batteries.

Origin of Performance Improvements in Lithium‐Ion Cells after Fast Formation

AbstractThe formation process of lithium‐ion batteries commonly uses low current densities, which is time‐consuming and costly. Experimental studies have already shown that slow formation may neither be necessary nor beneficial for cell lifetime and performance. This work combines an experimental formation variation with physicochemical cell and solid electrolyte interphase (SEI) modeling to reveal formation‐induced changes within the cells. Formation at C/2 without full discharge compared to a standard C/10 formation at 20 °C notably improves the discharge and charge capacities at 2C by up to 41 % and 63 %, respectively, while reducing the formation time by over 80 %. Model‐based cell diagnostics reveal that these performance gains are driven by improved transport in the anode electrolyte phase, which is affected by SEI formation, and by enhanced transport on the cathode side. Hence, the focus on the dense SEI layer is insufficient for a comprehensive understanding and, ultimately, optimization of cell formation. All formation procedures were also tested at temperatures of 35 °C and 50 °C. Despite often surpassing the 2C discharge capacity of the standard formation at 20 °C, these cells showed comparable or lower 2C charge capacities. This suggests a pivotal role of local temperature in the formation of large‐format cells.

NaBix/NaVyOz Hybrid Interfacial Layer Enables Stable and Dendrite-Free Sodium Anodes.

The challenges of sodium metal anodes, including formation of an unstable solid-electrolyte interphase (SEI) and uncontrolled growth of sodium dendrites during charge-discharge cycles, impact the stability and safety of sodium metal batteries. Motivated by the promising commercialization potential of sodium metal batteries, it becomes imperative to systematically explore innovative protective interlayers specifically tailored for sodium metal anodes. In this work, a NaBix/NaVyOz hybrid and porous interfacial layer on sodium anode is successfully fabricated via pretreating sodium with bismuth vanadate. The hybrid interlayer effectively combines the advantages of sodium vanadates and alloys, raising a synergistic effect in facilitating sodium deposition kinetics and inhibiting the growth of sodium dendrites. As a result, the modified sodium electrodes (BVO-Na) can stably cycle for 2000h at 0.5mAcm-2 with a fixed capacity of 1mAhcm-2, and the BVO-Na||Na3V2(PO4)3 full cell sustains a high capacity of 94 mAh g-1 after 600 cycles at 5C. This work demonstrates that constructing an artificial hybrid interlayer is a practical solution to obtain high performance anodes in sodium metal batteries.

Fluorine Rich Borate Salt Anion Based Electrolyte for High Voltage Sodium Metal Battery Development.

This study demonstrates the enhanced performance in high-voltage sodium full cells using a novel electrolyte composition featuring a highly fluorinated borate ester anion (1M Na[B(hfip)4].3DME) in a binary carbonate mixture (EC:EMC), compared to a conventional electrolyte (1M Na[PF6] EC:EMC). The prolonged cycling performance of sodium metal battery employing high voltage cathodes (NVPF@C@CNT and NFMO) is attributed to uniform and dense sodium deposition along with the formation of fluorine and boron-rich solid electrolyte interphase (SEI) on the sodium metal anode. Simultaneously, a robust cathode electrolyte interphase (CEI) is formed on the cathode side due to the improved electrochemical stability window and superior aluminum passivation of the novel electrolyte. The CEIs on high-voltage cathodes are discovered to be abundant in C-F, B-O, and B-F components, which contributes to long-term cycling stability by effectively suppressing undesirable side reactions and mitigating electrolyte decomposition. The participation of DME in the primary solvation shell coupled with the comparatively weaker interaction between Na+ and [B(hfip)4]- in the secondary solvation shell, provides additional confirmation of labile desolvation. This, in turn, supports the active participation of the anion in the formation of fluorine and boron-rich interphases on both the anode and cathode.

Effects of Electrolyte Solvent Composition on Solid Electrolyte Interphase Properties in Lithium Metal Batteries: Focusing on Ethylene Carbonate to Ethyl Methyl Carbonate Ratios

This study investigated the influence of variations in the mixing ratio of ethylene carbonate (EC) to ethyl methyl carbonate (EMC) on the composition and effectiveness of the solid electrolyte interphase (SEI) in lithium-metal batteries. The SEI is crucial for battery performance, as it prevents continuous electrolyte decomposition and inhibits the growth of lithium dendrites, which can cause internal short circuits leading to battery failure. Although the properties of the SEI largely depend on the electrolyte solvent, the influence of the EC:EMC ratio on SEI properties has not yet been elucidated. Through electrochemical testing, ionic conductivity measurements, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, the formation of Li2CO3, LiF, and organolithium compounds on lithium surfaces was systematically analyzed. This study demonstrated that the EC:EMC ratio significantly affected the SEI structure, primarily owing to the promotion of the formation of a denser SEI layer. Specifically, the ratios of 1:1 and 1:3 facilitated a uniform distribution and prevalence of Li2CO3 and LiF throughout the SEI, thereby affecting cell performance. Thus, precise control of the EC:EMC ratio is essential for enhancing the mechanical robustness and electrochemical stability of the SEI, thereby providing valuable insights into the factors that either enhance or impede effective SEI formation.

Formation of solid electrolyte interphase in Li-ion batteries: Insights from temperature-accelerated ReaxFF molecular dynamics

The solid electrolyte interphase (SEI) forms between anode and electrolyte in the lithium-ion battery (LIB) and is considered to be the main contributor to LIB degradation. To understand the degradation and SEI formation, we use reactive force-field (ReaxFF) molecular dynamics to gain atomic level insights into the key phenomena. We report the effect of different reaction temperatures on SEI formation on the lithium metal anode surface in contact with pure ethylene carbonate electrolyte. The temperature elevation is found to boost the SEI formation. To investigate the structural variations of SEI, we compare the quantitative variations of key species and perform analysis using the charge distribution and radial distribution function (RDF). Our work reveals that elevated temperature of up to 700 K is appropriate for acceleration of chemical reactions during SEI formation. The study provides insights into structural variations of the lithium metal electrode and SEI at the molecular level, demonstrating that temperature-accelerated reactive molecular dynamics is an efficient and effective tool for predicting the performance and degradation of the Li-ion batteries.

A novel efficient three-stage electrochemical pre-lithiation method for the amorphous carbon negative electrodes of lithium-ion capacitors

Electrochemical pre-lithiation stands as a practical and widely adopted technique for precisely controlling the degree of pre-lithiation, but the process is usually time-consuming. Herein, we introduce a novel three-stage electrochemical pre-lithiation method, comprising an initial stage of a high current density, a second stage of a low current density, and an additional stage of constant voltage to ensure the complete formation of solid electrolyte interphase (SEI) on the amorphous carbons: soft carbon (SC) and hard carbon (HC). Lithium-ion capacitors (LICs) are configured with the pre-lithiated SC or HC as the negative electrode and activated carbon as the positive electrode to assess the efficacy and adaptability of this three-stage pre-lithiation approach. Our findings demonstrate that this method can reduce the pre-lithiation time from 1114 to 604 min for SC, and from 1913 to 1080 min for HC, achieving nearly 46 % and 44 % decreases, respectively. Furthermore, the three-stage pre-lithiation method can simultaneously increase reversible Li-ion storage capacity within the same operating potential window, thereby enhancing the electrochemical performance of the LIC cells. Specifically, the LIC cell employing the three-stage pre-lithiated SC exhibits an energy density of 96.5 Wh kg-1 at 0.15 kW kg-1 and 76.5 Wh kg-1 at 5.98 kW kg-1. These cells demonstrate remarkable reversibility, retaining 89.6 % charge capacity after 10,000 cycles. Similarly, the LIC with the three-stage pre-lithiated HC achieves even higher energy densities of 105.3 Wh kg-1 at 0.15 kW kg-1 and 86.42 Wh kg-1 at 5.98 kW kg-1 with a retention of 85.2 % after 5000 cycles. The successful implementation and validation of this three-stage pre-lithiation method pave the way for further development of LICs.

Fluorinated Surface Engineering towards High-rate and Durable Potassium-ion Battery.

Solid electrolyte interphase (SEI) crucially affects the rate performance and cycling lifespan, yet to date more extensive research is still needed in potassium-ion batteries. We report an ultra-thin and KF-enriched SEI triggered by tuned fluorinated surface design in electrode. Our results reveal that fluorination engineering alters the interfacial chemical environment to facilitate inherited electronic conductivity, enhance adsorption ability of potassium, induce localized surface polarization to guide electrolyte decomposition behavior for SEI formation, and especially, enrich the KF crystals in SEI by self-sacrifice from C-F bond cleavage. Hence, the regulated fluorinated electrode with generated ultra-thin, uniform, and KF-enriched SEI shows improved capacity of 439.3 mAh g-1 (3.82 mAh cm--2), boosted rate performance (202.3 mAh g-1 at 8.70 mA cm-2) and durable cycling performance (even under high loading of ~8.7 mg cm-2). We expect this practical engineering principle to open up new opportunities for upgrading the development of potassium-ion batteries.