Stable Solid Electrolyte Interphase Layer Research Articles

Recent Progress of Advanced Functional Separators in Lithium Metal Batteries.

As a representative in the post-lithium-ion batteries (LIBs) landscape, lithium metal batteries (LMBs) exhibit high-energy densities but suffer from low coulombic efficiencies and short cycling lifetimes due to dendrite formation and complex side reactions. Separator modification holds the most promise in overcoming these challenges because it utilizes the original elements of LMBs. In this review, separators designed to address critical issues in LMBs that are fatal to their destiny according to the target electrodes are focused on. On the lithium anode side, functional separators reduce dendrite propagation with a conductive lithiophilic layer and a uniform Li-ion channel or form a stable solid electrolyte interphase layer through the continuous release of active agents. The classification of functional separators solving the degradation stemming from the cathodes, which has often been overlooked, is summarized. Structural deterioration and the resulting leakage from cathode materials are suppressed by acidic impurity scavenging, transition metal ion capture, and polysulfide shuttle effect inhibition from functional separators. Furthermore, flame-retardant separators for preventing LMB safety issues and multifunctional separators are discussed. Further expansion of functional separators can be effectively utilized in other types of batteries, indicating that intensive and extensive research on functional separators is expected to continue in LIBs.

Correlation between surface/bulk properties and electrochemical cycling performance of pure silicon anode materials

State-of-the-art lithium-ion batteries (LIBs) employ silicon (Si)-graphite composite anode with just a few percentages of Si active material, whose cycle-life relies on a stable solid electrolyte interphase (SEI) layer. As a number of various types of industrial Si active materials are currently available, an informative guideline based on the material properties and resultant cycling performance of different pure Si (i.e., without graphite) anode materials is strongly needed for material selection. The present study provides for the first time the correlation among material's surface and bulk properties, the SEI formation behavior, and cycling behavior of highly loaded pure Si anodes (2.3 mAh cm−2) prepared from four different industrial active materials, which are SiOx, carbon-coated Si, and bare Si with submicron and micron sizes. Commercial electrolyte with 10 wt% fluoroethylene carbonate additive is used for electrochemical performance evaluation. Based on solid-state NMR, XPS, and electrochemical analysis results, SiOx is determined to be relatively beneficial for practical applications beyond Si materials, in the aspects of high structural and particle morphology stability, cycling stability and suppressed interfacial resistance. This is mainly because of more effective accommodation of volume change of Si and oxygen-enriched surface (SEI) stability. The data give insight into the rational design of well-working Si-dominant or pure Si anodes for high energy density LIBs.

Enhancing low-temperature electrolyte performance through intermittent discharge for improved LiODFB additive film formation

The challenge of improving low-temperature performance in lithium-ion batteries (LIBs) is attributed to the formation of an unstable solid electrolyte interphase (SEI) film. Lithium difluoro(oxalate)borate (LiODFB) has demonstrated potential in enhancing capacity retention and reducing impedance at low temperatures by establishing a high ion conductivity and stable SEI layer. Previous research indicates that the BOF2− anion, a soluble product of film formation additive of LiODFB hinder salt decomposition by aggregating on the electrode surface. This study presents a strategy to intensify the film formation process of LiODFB additives by introducing an optimal standing time during intermittent discharge processes. Three specific stages of soluble product diffusion are discussed. Diffusion starts from the outer layer of adsorption composed of soluble substances, gradually extends to the inner layer of adsorption, and finally establishes a new connection with the electrode. A brief standing time proves insufficient for inner adsorption layer diffusion, while excessively extended standing time fails to accelerate LiODFB decomposition. A standing time of 2300 s is selected to promote a stable SEI layer. This strategy elevates the capacity retention rate of cells at –20 °C from 66.59 % to 84.44 %. The study offers a method to address battery performance degradation in low-temperature conditions.

MOF-Derived Bimetallic Selenide CoNiSe2 Nanododecahedrons Encapsulated in Porous Carbon Matrix as Advanced Anodes for Lithium-Ion Batteries.

Transition metal selenides have received considerable attention as promising candidates for lithium-ion battery (LIB) anode materials due to their high theoretical capacity and safety characteristics. However, their commercial viability is hampered by insufficient conductivity and volumetric fluctuations during cycling. To address these issues, we have utilized bimetallic metal-organic frameworks to fabricate CoNiSe2/C nanodecahedral composites with a high specific surface area, abundant pore structures, and a surface-coated layer of the carbon-based matrix. The optimized material, CoNiSe2/C-700, exhibited impressive Li+ storage performance with an initial discharge specific capacity of 2125.5 mA h g-1 at 0.1 A g-1 and a Coulombic efficiency of 98% over cycles. Even after 1000 cycles at 1.0 A g-1, a reversible discharge specific capacity of 549.9 mA h g-1 was achieved. The research highlights the synergistic effect of bimetallic selenides, well-defined nanodecahedral structures, stable carbon networks, and the formation of smaller particles during initial cycling, all of which contribute to improved electronic performance, reduced volume change, increased Li+ storage active sites, and shorter Li+ diffusion paths. In addition, the pseudocapacitance behavior contributes significantly to the high energy storage of Li+. These features facilitate rapid charge transfer and help maintain a stable solid-electrolyte interphase layer, which ultimately leads to an excellent electrochemical performance. This work provides a viable approach for fabricating bimetallic selenides as anode materials for high-performance LIBs through architectural engineering and compositional tailoring.

Facile Fabrication of Polymer Electrolytes with Branched Structure via Deep Eutectic Electrolyte-Enabled In Situ Polymerizations.

The demand for higher energy density in energy storage devices drives further research on lithium metal batteries (LMBs) because of the high theoretical capacity and low voltage of lithium metal anode. Polymer electrolytes (PEs) exhibit obvious advantages in combating volatilization and leakage compared with liquid electrolytes, which improves the safety of LMBs. However, it is still difficult to construct PEs with a stable electrolyte-electrode interface for high-performance and long-term life LMBs. Herein, the gel polymer electrolyte (GPE-SL) containing deep eutectic electrolyte (DEE) and branchlike polymer skeleton are designed and prepared by the DEE-induced in situ cationic and radical polymerizations. The DEE provides a smooth Li+ migration pathway to ensure the electrochemical properties, and the multibrominated polymer matrix formed in situ enables a LiBr-rich solid electrolyte interphase (SEI) layer on lithium metal anode and prolongs the life span of LMBs. Hence, the Li|GPE-SL|LiFePO4 battery displays an excellent cycling stability with 84% capacity retention after 1200 cycles at 1C. This simple deep eutectic electrolyte-induced polymerization method provides a promising direction for high-performance LMBs with improved anode-electrolyte compatibility through the construction of a stable SEI layer in situ.

Three-dimensional dual-layered conductive binder enables stable and high performance of SiOx/C anodes

Among practical anode materials for next-generation lithium-ion batteries (LIBs), SiOx has garnered substantial attention owing to its relatively low volumetric variation and high theoretical capacity. Nevertheless, the volumetric change of micro-SiOx remains a formidable challenge for existing adhesives. Here, we propose an innovative design strategy that amalgamates both rigidity and flexibility, in which rigid anion gum Arabic (GA), flexible acrylic random copolymer (ARC), and carbon nanotubes (CNTs) interwoven into a 3D network with strong interfacial adhesion and excellent mechanical properties. These attributes effectively restrict SiOx particles and favor a stable solid electrolyte interphase (SEI) layer formed on SiOx. Here, GA plays a pivotal role in dispersing CNTs and maintaining their consistent proximity to SiOx, thereby establishing stable electron conduction networks. The SiOx electrode still sustains a specific capacity of 760 mAh g−1 after 350 cycles under a high current of 1C. Additionally, at 0.2C, the SiOx electrode attains a notably high capacity of 1105 mAh g−1 with a capacity retention of 72.9 % at the 300th cycle, while exhibiting an excellent areal capacity of 1.4 mAh cm−2 even after 400 cycles. This work develops a straightforward yet highly efficacious approach for fabricating high areal capacity electrodes and offers promising prospects for improving the stableness of Si-based anodes.

Approach for Mitigating Interfacial Degradation in Silicon-Based Electrodes to Enhance Cycling Stability of Lithium-Ion Batteries and Capacitors

The growing demand for high energy density in lithium-ion batteries has led to extensive investigations on silicon negative electrodes. In this study, we propose a novel approach to address the interfacial degradation of electrodes caused by volume expansion during lithium insertion/extraction. The approach involves a sandwich structure consisting of a carbon nanofiber (CNF) undercoating electrode and a CNF-coated separator. The CNF is treated with acid to form carboxyl and hydroxyl groups on its surface, which improves the dispersion of the coating slurry and enhances adhesion to the electrode. Through electrochemical testing, the improved silicon electrode shows a high retention rate of 82% compared to the initial capacity after 100 cycles, and high electrochemical performance when applied to both lithium-ion batteries and lithium-ion capacitors. These results are attributed to the improved adhesion between the electrode and current collector, as well as the formation of a stable solid electrolyte interphase layer on the electrode surface. These findings suggest that the conductive coating process, applied to the separator and current collector, effectively mitigates interfacial issues that are associated with silicon-based electrodes. This approach has the potential to overcome the degradation characteristics of silicon electrodes and significantly contribute to improving the cycling stability of lithium-ion batteries and capacitors.

Modulation of Prelithiation Solution for Hard Carbon Anodes of Lithium-Ion Batteries

The increasing demand for high-energy and high-power lithium-ion batteries (LIBs) in portable gadgets and electric vehicles has led to exploration of high-performance silicon and hard carbon (HC) anodes to replace traditional graphite anodes. However, their practical application is hindered by low initial coulombic efficiency and large irreversible capacity, which decreases the total energy density. Prelithiation is a strategy to restore energy density by supplying additional Li ions. Chemical prelithiation, involving immersing the electrode in a reductive Li−aromatic hydrocarbon (arene) complex solution, is a standout method due to its safety, high efficiency, and practical feasibility. It not only restores the lost lithium but also aids in maintaining a more stable solid electrolyte interphase layer to guarantee battery cycling stability. The first part of our study addresses the issue of expensive and impractical arene complexes for prelithiation, we focus on using low-cost and commercially available aromatic compounds such as naphthalene and methyl-substituted naphthalene compounds. This study investigates the effects of electron-donating methyl groups on naphthalene on the prelithiation activity toward HC using density functional theory calculations. In the second part of this study, we use low-cost and easily available solvents such as ethylene glycol dimethyl ether, bis(2-methoxyethyl) ether, and triethylene glycol dimethyl ether for chemical prelithiation. Ether solvents have a desirable solvation effect with Li+, and the ether with low solvation power enhances the prelithiation activity. The degree of prelithiation is greatly affected by the reaction time, and the details of this relationship are rarely investigated. In the final part of our study, we conduct a detailed investigation on the effects of various reaction times on the prelithiation activity toward the HC anode. This study provides useful insights for effective prelithiation, in terms of choosing aromatic compounds, solvents, and reaction time.

Enhancing Cycle Life of Lithium Metal Batteries By Regulating Solid-Electrolyte Interphase Using Gel Polymer Electrolyte

Lithium metal with high theoretical capacity and low redox potential is one of the promising anode materials for high energy density batteries. However, the lithium metal has safety problems and poor cycling performance, due to the growth of Li dendrite and side reactions between Li and electrolytes. One of the most effective strategies to stabilize Li metal is forming robust solid-electrolyte interphase (SEI). Recently, anion-derived and inorganic-rich SEI is known to be stable and ionic conductive, leading to good cycling stability. One of the most popular strategies to form durable SEI is to use the localized high-concentration electrolytes (LHCE) which construct an anion-derived SEI layer on Li metal. In this work, we synthesized LHCE-based gel polymer electrolytes to form a stable SEI layer and enhance cycling stability. Small amount of cross-linking agent was added into dimethoxyethane (DME)-based LHCE when synthesizing gel polymer electrolyte. The functional groups in cross-linking agents increase Li+ and anion interaction in the gel polymer electrolytes, resulting in formation of the stable SEI layer. The solvation structure and chemical composition of the SEI layer were investigated by density functional theory (DFT) calculation and spectroscopic analyses such as FT-IR, Raman, and XPS. The Li/NCM811 cells with LHCE-based gel polymer electrolyte were assembled for the cycling test, and they exhibited superior cycling performance than liquid electrolyte-based cells.

Development of polycarbonate-based electrolytes with in situ polymerized electrolyte interlayers for lithium-metal batteries

Solid polymer electrolytes (SPEs), especially polycarbonate-based SPEs, have emerged as promising candidates for next-generation lithium-metal batteries (LMBs) due to their enhanced safety features and suitable mechanical and electrochemical properties. However, the limited interface compatibility between SPEs and electrodes, along with the persistent issue of lithium dendrite formation, hindered the progress of LMBs. In this study, an innovative approach is introduced to address these challenges by incorporating an in situ polymerized poly(vinyl ethylene carbonate) (PVEC) electrolyte interlayer between poly(ethylene carbonate) (PEC)-based SPE and electrode material. Furthermore, lithium nitrate (LiNO3) is incorporated as an additive in the PEC-based SPE to facilitate the formation of a stable and suitable solid electrolyte interphase (SEI) layer, thereby enhancing the cycling stability of LMBs. Notably, the Li||Li symmetric cell, equipped with the in situ PVEC electrolyte interlayer and the LiNO3-additive-containing PEC-based electrolyte, exhibited remarkable stability, maintaining a continuous cycling for 70 h at a current density of 0.1 mA cm−2. Similarly, a Li||LiFePO4 cell demonstrated impressive performance, sustaining 40 charge-discharge cycles at a current density of 0.1C (1C = 170 mA g−1) while maintaining a discharge capacity of approximately 150 mAh g−1. This work showcases a straightforward strategy for enhancing interfacial compatibility through in situ polymerization of the interlayer and the incorporation of electrolyte additives.

Electrode Parameterization as an Investigative Tool for Solid Electrolyte Interphase Evolution Monitoring on Commercial Lithium-Ion Battery Electrodes

The formation process is one of the most critical aspects of lithium-ion battery (LIB) production. It involves the creation of an interface layer known as solid electrolyte interphase (SEI). The layer predominantly forms during the first few charging cycles of the battery, resulting in approximately 10% capacity reduction [1]. However, forming a stable SEI layer is critical in ensuring uniform cell capacity, safe operation, and a long lifetime of LIBs [2].The thickening of the SEI layer is one of the main contributors to capacity fade over the battery lifetime and strongly depends on electrochemical cycling conditions [1]. Despite its importance, there are still no comprehensive theories and models describing SEI formation and evolution. The difficulties arising from its characterization could explain why various structure models have appeared in the literature [3–5]. Therefore, it is indispensable to go beyond traditional characterization methods to fully elucidate the SEI layer behaviours.In this work, we investigate changes in the kinetic and thermodynamic electrode parameters with growing SEI layer thickness, deriving relevant variables, such as exchange current density, electrode tortuosity, and lithium diffusion coefficient from experimental data. The measurements are performed on commercially relevant electrodes. Parameter evolution monitoring will contribute to developing a predictive understanding of the SEI layer evolution under different cycling conditions, and to unlocking improvements in LIB sustainability by prolonging their lifetime and enhancing safety.

Dual-Additive Approach for Tuning Si-Based Anode Interphase Realized By Operando ATR-FTIR

Dual-additive approach for tuning Si-based anode interphase realized by Operando ATR-FTIRMasoud Baghernejad1, Matthias Weiling1, Felix Pfeiffer1, Diddo Diddens1, Lars Frankenstein2, Christian Lechtenfeld2 1Helmholtz-Institute Münster, IEK-12, Forschungszentrum Jülich GmbH, Corrensstraße 46, 48149 Münster, Germany 2MEET Battery Research Center, Institute of Physical Chemistry, University of Münster, Corrensstraße 46, 48149 Münster, GermanySilicon is a promising next-generation anode material, offering a high gravimetric capacity. However, silicon-based anodes suffer from significant volume expansion during lithiation that can cause particle pulverization and capacity fade, continuous solid-electrolyte interphase (SEI) (re-)formation, and constant electrolyte consumption. To alleviate these issues, the effect of 2-Sulfobenzoic anhydride (2-SBA) as an SEI electrolyte additive was investigated through complementary electrochemical and operando spectroscopic techniques.The electrochemical performance was evaluated through galvanostatic charge/discharge cycling. The results show that the optimum concentration of 2-SBA improves the cycling stability and capacity retention of NMC811||AG+20% SiOx (4.5 – 2.8 V) cells to more than 100 cycles compared to 70 cycles with the baseline electrolyte (BE) before cell failure. Introducing lithium difluorophosphate (LiDFP), a common additive for high-voltage applications, to the electrolyte containing 2-SBA further increased the cycle life to 160 cycles. Interestingly, LiDFP alone in the electrolyte did not lead to improved electrochemical performance or longer cycle life of the cells compared to BE, proving a beneficial dual-additive approach of combining inorganic and organic compounds for sufficient SEI formation on AG+20% SiOx anodes. The analysis of the electrochemical performance concludes that the improved SEI structure formed by 2-SBA and LiDFP mitigates pulverization. In this regard, the SEI structure is further analyzed using operando ATR-FTIR spectroscopy.Operando ATR-FTIR spectroscopy proves to be a powerful technique in battery research, particularly for investigating SEI. The ATR mode's surface sensitivity enables studying the composition of the SEI without bulk signal interference. In this work, we employed the internal reflection mode of the ATR-FTIR spectroscopy, for which the electrode of interest has to be IR permeable. Furthermore, by variation of the incident angle of the IR beam, the penetration depth can be varied to obtain an interphase profile from electrode to bulk electrolyte. In this study, the SEI composition on the silicon anode in the presence of BE and the corresponding additives, 2-SBA and LiDFP, was investigated under real-working conditions. The results elucidate that 2-SBA is accumulated and decomposed via ring-opening on the silicon surface to form a stable SEI layer. However, in the presence of LiDFP and 2-SBA, a hybrid organic and inorganic SEI layer is formed, which proves to enhance electrochemical performance and cycle life. The findings of this study provide valuable structural insights into the silicon particle surface for the development of high-voltage silicon-based lithium-ion batteries with Ni-rich cathodes.

Insights into the SiO2 Stress Effect on the Electrochemical Performance of Si anode.

Silicon (Si) is regarded as the most potential anode material for next-generation lithium-ion batteries (LIBs). However, huge volume expansion hinders its commercial application. Here, a yolk-shell structural nitrogen-doped carbon coated Si@SiO2 is prepared by SiO2 template and HF etching method. The as-prepared composite exhibits superior cycling stability with a high reversible capacity of 577mA h g-1 at 1 A g-1 after 1000 cycles. The stress effect of SiO2 on stabilizing the electrochemical performance of Si anode is systematically investigated for the first time. In situ thickness measurement reveals that the volume expansion thickness of Si@SiO2 upon charge-discharge is obviously smaller than Si, demonstrating the electrode expansion can be effectively inhibited to improve the cyclability. The density functional theory (DFT) calculation further demonstrates the moderate young's modulus and enhanced hardness after SiO2 coating contribute significantly to the mechanical reinforcement of overall Si@SiO2@void@NC composite. Various post-cycling electrode analyses also address the positive effects of inner stress from the Si core on effectively relieving the damage to electrode structure, facilitating the formation of a more stable inorganic-rich solid electrolyte interphase (SEI) layer. This study provides new insights for mechanical stability and excellent electrochemical performance of Si-based anode materials.

Coordinated self-assembly of ultraporous 3D aramid nanofibrous separators with a poly(vinyl alcohol) sheath for lithium-metal batteries

Li-metal batteries with a low negative/positive electrode capacity ratio require significant improvement to ensure their practical implementation as high-energy-density batteries. In the present study, ultraporous aramid nanofiber (ANF) separators with a poly(vinyl alcohol) (PVA) sheath were fabricated using a coordinated self-assembly process to produce an ultrahigh bulk (>95 %) and surface (>48.6 %) porosity and a high ion affinity. In this process, sol films consisting of an optimized mixture of aramid nanoseed sols and PVA were sequentially immersed in ethanol and water to induce the formation of a 3D aramid network and the phase separation of PVA by their rate differences, followed by swelling-induced pore formation. The resulting separators exhibited an excellent ion conductivity and Li+ ion transference number of up to 2.73 mS cm−1 and 0.78, respectively, with the effective suppression of Li dendritic growth and the formation of a stable fluorine-rich solid electrolyte interphase (SEI) layer on the Li-metal surface. Li/Li half cells exhibited stable operation for up to 1500 cycles with a high current density of 10 mA cm–2 and an areal capacity of 1 mAh cm–2, with Li/Cu half cells operating for over 244 cycles even with a lithiophobic Cu current collector. LFP/Li full cells with a low N/P ratio (∼2.03) exhibited stable operation for 172 cycles with an average Coulombic efficiency of 99.6 %. NCM/Li full cell with extremely low N/P ratio (0.96) and lean electrolyte condition (4 g Ah–1) stably operated for 55 cycles with projected energy density of 350.7 Wh kg–1.

Temperature-dependent Viscoelastic Liquid MOFs Based Cellulose Gel Electrolyte for Advanced Lithium-Sulfur Batteries Over an Extensive Temperature Range

The uncontrolled growth of lithium dendrites severely limits the practical use of Li-S batteries. Additionally, cell temperature increases during operation, accelerating dendrite growth and side reactions. To stabilize the anode over a wide temperature range, we proposed a promising solution of a novel temperature-dependent viscoelastic liquid UiO66 MOFs-based cellulose gel electrolyte. This specially engineered electrolyte demonstrated superior stabilization of the anode. It adopted the “blocking anions and promoting Li+ transfer” strategy, resulting in a uniform Li+ flux deposition and the formation of a stable and dense solid electrolyte interphase layer, effectively suppressing dendrite growth. To further improve the cycling performance of the cell, a hollow transition bi-metal selenide (FeCo-Se2/NC) was developed as the sulfur host material. This complex exhibited a strong chemisorption capacity for polysulfides and a high catalytic ability to expedite the conversion process of lithium polysulfides. The final cell achieved a high capacity of 687.2 mAh g−1 after 500 cycles at 3 C with a minimal fading rate of 0.04% per cycle. It also demonstrated a high area capacity of 5.78 mAh cm−2 at a high sulfur loading of 6.2 mg cm−2, along with excellent cycling stability under temperature-varying conditions. The findings not only highlighted the commercialization potential of Li-S batteries but also underscored the effectiveness of porous liquid MOFs as a modified layer, effectively stabilizing the Li anode and reducing interfacial impedance between the electrolyte and electrode. Our research paved the way for advanced energy storage solutions that could significantly contribute to a sustainable and eco-friendly future.

Transforming Dye Molecules into Electrochemical Allies: Direct Red 80 as a Dual-Functional Electrolyte Additive for Dendrite-Free Aqueous Zinc-Ion Batteries.

Despite the numerous advantages of abundant zinc resources, low redox potential, and affordability, aqueous zinc-ion batteries (AZIBs) currently face limitations due to dendritic growth and side reactions. This study explores the use of low-cost and efficient anionic dyes, specifically Direct Red 80 (DR80) as dual-functional electrolyte additives to enhance the electrochemical performance of AZIBs and facilitate the reuse of dye wastewater. Experimental and theory calculation results all demonstrate that the DR80 molecules readily adsorb onto the surface of the zinc anode, creating a stable and robust solid electrolyte interphase layer. This layer acts as a protective barrier, effectively mitigating H+ attacks and reducing both hydrogen evolution and corrosion reactions. Additionally, it covers any initial protrusions on the zinc anode, preventing the occurrence of the "tip-effect" phenomenon and limiting access of water to the zinc anode, thereby minimizing water decomposition. Moreover, the sulfonic acid groups of DR80 molecules displace some water molecules in [Zn(H2O)6]2+, disrupting the original solvent sheath and reducing water decomposition. Especially, using the DR80 additive, the Zn/Zn cell reaches an impressive cycle life of 1500 h at 2 mA cm-2@1 mAh cm-2. Given the low cost and widespread availability, this additive shows great potential in the future practical implementation of AZIBs.

Zwitterion as electrical double layer regulator to in-situ formation of fluorinated interphase towards stable zinc anode

The issues of serious corrosion and dendrite growth in electrode surface hinder the commercialization of aqueous zinc batteries. A stable solid electrolyte interphase (SEI) on electrode surface is critical to improve electrochemical performance of Zn anode. Here, a novel zwitterion additive as an electrical double layer (EDL) regulator with SEI-forming capability is developed. The zwitterion exhibits preferential adsorption with Zn anode to construct a fast Zn2+ migration channel. More importantly, a ZnF2 SEI layer can be in-situ generated on the anode due to preferential electroreduction of zwitterion, which isolates Zn anode from electrolytes. Therefore, the symmetric cells with the proposed electrolyte survive long cycling stability over 600 h at 10 mA cm−2 and 10 mAh cm−2. The merits of zwitterion additive are further demonstrated in the Zn||V2O5·nH2O full cell with a capacity retention of ∼80 % after 1000 cycles.

Robust Interfacial Chemistry Induced by B‐Doping Enables Rapid, Stable Sodium Storage

AbstractConstructing a stable solid electrolyte interphase (SEI) at the electrode–electrolyte interface is powerful for optimizing the battery performance. However, studies related to interface chemistry have particularly focused on engineering electrolytes and overlooked regulating electrode materials. Here, this study reports that the B‐doped Bi interconnected nanoparticles (B─Bi) are prepared by a facile and effective chemical reduction reaction. The B doping helps to catalyze the electrolyte decomposition and more NaF formation on the electrode surface, which facilitates a stable uniform SEI with enhanced mechanical stability. Such a robust SEI layer can inhibit the further decomposition of electrolytes and promote the interfacial Na+ transfer. The B─Bi offers a reversible capacity of 403.1 mAh g−1 at 1.0 A g−1 and a high rate capability of 203 mAh g−1 at 80 A g−1. Moreover, the B‐doping method also finds its viability to stabilize SEI in Sb material. This study demonstrates a new strategy for engineering the interface chemistry toward stable SEI and excellent performance.

The effect of Ti-based surface layer on AlSi thin film as a high-performance anode for the lithium-ion battery

Significant volume changes during cycling and the instability of the solid electrolyte interphase (SEI) are the main challenges that limit the practical application of silicon-based anodes. TiN and TiO2 were selected as surface layers and deposited on the HCl-etched AlSi (AlSi’) thin films by atomic layer deposition (ALD) to enhance the electrochemical performance of the anode. The surface layers with excellent mechanical strength can effectively suppress the volume expansion of the AlSi thin film and maintain excellent electrical contact between the film and the substrate during cycling. The effects of TiN and TiO2 surface layers on the composition and growth of the SEI layer on the AlSi’ film anode have been discussed in detail. The TiO2 surface layer was found to inhibit the continuous growth of the SEI layer and promote the formation of a mechanically robust and stable SEI layer. The AlSi’/TiO2(8 nm) anode shows a high initial discharge capacity of 2802 mA h g-1 with an initial coulomb efficiency (ICE) of 88% at 0.8 A g-1, and it maintains a capacity retention rate of 83% after 500 cycles. Moreover, the AlSi’/TiO2(8 nm) anode exhibits outstanding rate performance, as it sustains a capacity of 1710 mA h g-1 after 500 cycles at 5 A g-1, and maintains a capacity above 1032 mA h g-1 even at 30 A g-1.

Three dimensional titanium dioxide nanotube arrays induced nanoporous structures and stable solid electrolyte interphase layer for excellent sodium storage in ether-based electrolyte

The commercial feasibility of sodium ion batteries (SIBs) is currently limited by the lack of anode materials that simultaneously provide high-rate capability and long cycle stability. In this study, we report three-dimensional (3D) anatase TiO2 nanotube arrays (TiO2 NTAs) as an SIB anode for excellent sodium storage when paired with ether-based electrolyte. The TiO2 NTAs anode exhibits minimal capacity decay over 3000 cycles at 1C and 5000 cycles at 20C in ether-based electrolyte, demonstrating both excellent rate capability and long-term cycle stability. Structural analysis reveals novel discovery that the 3D TiO2 NTAs develop into unique nanoporous structures that sustain during repeated redox cycles in ether-based electrolyte. On the one hand, these nanoporous structures can provide more accessible areas for Na+ intercalation and de-intercalation, enabling fast Na+ intercalation. On the other hand, they also promote the formation of a thin and stable solid electrolyte interphase (SEI) in ether-based electrolyte that facilitates long-term cycle stability. Our investigation advances the performance of TiO2 as a promising SIBs anode material and also offers valuable insights into the impact of unique nanoporous structure to the excellent electrochemical performance.