Surface Chemistry Research Articles

Surface Iodide Defects Control the Kinetics of the CsPbI3 Perovskite Phase Transformation.

Halide perovskites are technologically interesting across a wide range of optoelectronic devices, especially photovoltaics, but material stability has proven to be challenging. One degradation mode of note is the meta stability of the perovskite phase of some material compositions. This was studied by tracking the change of CsPbI3 from its optoelectronically relevant perovskite phase to its thermodynamically stable nonperovskite phase, δ-CsPbI3. We explore kinetics as a function of surface chemistry and observe a quantitatively similar, ∼5-fold, reduction in the phase transition rate between neat films and those treated with CsI and CdI2. Using XPS to explore surface chemistry changes across samples, we link the reduction in the phase transition rate to the surface iodide concentration. When informed by previous theoretical studies, these experiments point to surface iodide vacancies as the nucleation sites for δ-CsPbI3 growth and show that phase nucleation is the rate limiting step in δ-CsPbI3 formation for CsPbI3 perovskite thin films.

Adsorption of nickel (II) from aqueous solutions with clay-supported nano-scale zero-valent iron synthesized from green tea extract

Nano zerovalent iron (nZVI) supported adsorbents have been reported as suitable candidates for adsorption of water contaminants. However, the role of and interplay between surface chemistry, functional group density and textural properties has largely been unexplored. In this work, green tea derived nano zerovalent iron (nZVI) supported clay hybrid material (CnZVI) was used as a novel adsorbent for the removal of Ni2+ ions from water. The unmodified natural clay (Arg) and the CnZVI composite were characterized using FTIR, SEM, TGA and BET techniques. Incorporation of nZVI ameliorated the specific surface area from 16.88 to 30.46 m2/g, translating to ∼80 % increase. This translated to ∼69 % increase in maximum adsorption capacity from 8.47 to 14.38 mg/g, respectively. The addition of nZVI in the clay decreased the affinity (KF) for Ni2+ by ∼48 %. The disparity between the percent increase in surface area (∼80 %) and the adsorption capacity (∼69 %) implies the adsorption of Ni2+ was significantly controlled by textural properties compensating for the antagonistic effects of functional group density. The kinetic rates were best predicted by the pseudo-first-order and Elovich’s models for the Arg and CnZVI, respectively, implicit evidence of the role of surface chemistry. A maximum adsorption capacity of 14 mg/g was achieved for 100 mg Ni2+/L in 120 min for CnZVI.

Design & automation of a small-scale towing tank for flow visualization

Although the towing tank is a standard piece of equipment used to investigate fluid phenomena, it primarily exists as custom-built hardware that takes up a significant footprint. The size, cost, and custom-built nature have heretofore inhibited the production of this equipment in the authors’ context, an African university. This paper presents a small-scale (1000 mm x 200 mm x 200 mm), low-cost (<$1,000) towing tank made using readily available components and basic digital fabrication tools. Other universities on the continent and beyond can hence create this foundational platform for fluid mechanics-related teaching and research. Leveraging an Arduino microcontroller loaded with the GRBL firmware, G-code is sent from the computer to stepper motors to execute movements in two axes. This allows for automation capabilities, controlled towing speeds, and consistent experimental conditions. Validation tests revealed motion accuracy within 1 %. A glitter-based flow visualization approach to measuring surface phenomena is demonstrated here. Experiments conducted successfully visualized relevant flow characteristics generated by bluff bodies being towed in the tank. As the Reynolds number increased within the operating range, wider wakes and larger, more distinct vortices were generated, as expected. This platform can be replicated widely in institutions that may otherwise forego experimentation in fluid mechanics.

Hyperbranched Poly-l-Lysine Modified Titanium Surface With Enhanced Osseointegration, Bacteriostasis, and Anti-Inflammatory Properties for Implant Application: AnExperimental InVivo Study.

This study aimed to explore multiple effects of hyperbranched poly-l-lysine (HBPL) titanium (Ti) surfaces on osseointegration, bacteriostasis, and anti-inflammation across three different animal models. Ti surfaces were covalently modified with HBPL, with uncoated surfaces as controls. Characterization included scanning electron microscopy (SEM) and surface chemistry and elemental analysis (EDX). Ti and Ti-HBPL implants were placed in conventional canine edentulous sites, post-operative infection canine edentulous sites, and diabetic rat tibias. Implants from canine edentulous models were analyzed using micro-CT and histomorphometry to assess osseointegration at 8 weeks. Post-operative infection beagles were used to evaluate antibacterial efficacy through clinical parameters and bacterial cultures at 1 week. In diabetic rats, micro-CT and histomorphometry were performed at 8 weeks. HBPL was uniformly grafted on Ti-HBPL surfaces. Ti-HBPL surfaces showed higher bone volume/total volume (BV/TV, p < 0.001), bone-implant contact (BIC%, p < 0.001), and trabecular number (Tb.N, p < 0.01) in beagles. Besides, it displayed higher BIC% (p < 0.001) and bone area fraction occupancy (BAFO%, p < 0.01) in hard tissue sections. In an infected model, Ti-HBPL surfaces exhibited lower bleeding on probing (BOP, p < 0.001), and plaque index (DI, p < 0.01), with reduced bacterial colony formation (p < 0.001) compared to the control group. In diabetic rats, Ti-HBPL surfaces showed an increase in BV/TV (p < 0.01) and Tb.N (p < 0.001), downregulated TNF-α and IL-1β (p < 0.01), and upregulated IL-10 (p < 0.01) and osteocalcin (OCN) expression (p < 0.01). HBPL-Ti surfaces demonstrated enhanced osseointegration, bacteriostasis, and anti-inflammatory effects invivo.

The effect of phosphoric acid on the properties of activated carbons made from Myrtus communis leaves: Textural characteristics, surface chemistry, and capacity to adsorb methyl orange

In this work, chemical activation was employed to produce activated carbons and assess the impact of phosphoric acid (H3PO4) on their physicochemical properties. Using Myrtus communis Leaves (MC-Leaves) as the precursor and varying H3PO4 impregnation ratios (30 %, 60 %, 100 %, and 150 wt.%). The activation was conducted at 450 °C (10 °C/min) for 1 h in a room atmosphere. The effects of H3PO4 were evaluated through various techniques, including BET surface area analysis, FESEM-EDS imaging, XPS, FT-IR-ATR, Raman spectroscopy, CHNS-(O) elemental analysis, and Methyl orange (MO) adsorption studies. The specific surface area (SSA) and total pore volume increased from 642m2/g to 1237m2/g, total pore volume increased from 0.29cm3/g to 0.97cm3/g, and the mean pore diameter increased from 1.9 nm to 3.2 nm by increasing the impregnation ratio from 30 wt.% to 150 wt.%. The pH(pzc) of MC-ACs exhibited an acidic character, owing to the presence of oxygen-containing functional groups such as hydroxyl, carboxyl, metaphosphate (-PO3-), phosphates, and pyrophosphate groups, as indicated by XPS and FT-IR analysis. At a room temperature of 22 °C and an ideal pH of 2.06, the maximum adsorption capacity (qmax) rose from 46.02±4.63 mg g-1 to 326.54±37.67 mg g-1 as the impregnation ratio increased from 30 wt.% to 150 wt.%. Freundlich isotherm well explained the adsorption equilibrium at 22 °C for all MC-ACs. The effect of temperature illustrates that the adsorption of MO onto MC-AC30 % was endothermic, while the adsorption of MO onto MC-AC150 % was an exothermic. The kinetic study was conducted at 22 °C, when the equilibrium time was at 4hours, and it was a pseudo-second order (PSO) model.

Blobs form during the single-file transport of proteins across nanopores

The transport of biopolymers across nanopores is an important biological process currently under investigation for the rapid analysis of DNA and proteins. While the transport of DNA is generally understood, methods to induce unfolded protein translocation have only recently been discovered (Yu et al., 2023, Sauciuc et al., 2023). Here, we found that during electroosmotically driven translocation of polypeptides, blob-like structures typically form inside nanopores, often obstructing their transport and preventing addressing individual amino acids. This is in contrast with the electrophoretic transport of DNA, where the formation of such structures has not been reported. Comparisons between different nanopore sizes and shapes and modifications by different surface chemistries allowed formulating a mechanism for blob formation. We also show that single-file transport can be achieved by using 1) nanopores that have an entry and an internal diameter smaller than the persistence length of the polymer, 2) nanopores with a nonsticky (i.e., nonaromatic) inner surface, and 3) moderate translocation velocities. These experiments provide a basis for understanding polypeptide transport under confinement and for improving the design and engineering of nanopores for protein analysis.

Surface chemistry and catalytic activity in H2O2 decomposition of pyrolytically fluoralkylated activated carbons.

According to the proposed pyrolytic method, granular activated carbon (AC) Norit 830 W was functionalized by thermal treatment of AC in hydrofluorocarbon (HFC) gases, pentafluoroethane and 1,1,1,2-tetrafluoroethane, at 400-800 °C. This method does not require activation by plasma and photons. Chemical and elemental analysis showed that the pyrolytic treatment provides a loading of 2.95 mmol (5.6 wt%) of fluorine per gram of AC. Nitrogen adsorption measurements indicated that the microporous structure contracted when AC was treated with HFC at temperatures above 400 °C. Thermogravimetry, Fourier transform infrared spectroscopy (FTIR) with attenuated total reflectance (ATR), and X-ray photoelectron spectroscopy (XPS) demonstrated the evolution of oxygen-containing and fluorine-containing groups to more thermostable groups with treatment temperature. The fluorine-containing groups grafted at high temperature, above 600 °C exhibited the highest thermal stability up to 1250 °C in dry argon. From the data of XPS and solid-state 19F nuclear magnetic resonance spectroscopy data, the grafted fluorine exists in several types of grafted F-containing groups, the HFC residues. By changing the thermal regime of fluorination, the composition of fluorine-containing groups on a carbon surface can be regulated. Isolated fluoroalkyl groups can be grafted at temperatures of 400-500 °C, while at 600 °C and above, the semi-ionic fluorine groups increase significantly. The hydrophobized surface demonstrated the ability to effectively decompose H2O2 in methanol solutions.

Converting palm fatty acid distillate into solid adsorbents through zinc chloride activation

Water pollution is a critical environmental concern, and this study explores the potential of utilizing adsorbents from palm fatty acid distillate (PFAD) for the removal of methylene blue (MB) and congo red (CR) dyes from aqueous solution. The PFAD, a by-product of palm oil refining is a valuable adsorbent feedstock because it is freely available, abundant and high in carbon content. The PFAD adsorbents were synthesized via zinc chloride activation and characterized for elemental composition, specific area, surface chemistry and morphology. The process converts the semi-solid PFAD into solid adsorbents with surface area ranging from 22 m2/g to 222 m2/g. The specific area significantly increased with pyrolysis temperature, and so the adsorption of dyes. The results provide insights into the viability of PFAD adsorbents for effective removal of MB and CR dyes. Nonetheless, the process optimization and the true potential of PFAD adsorbents should be further explored.

Fluorinated ester additive to regulate nucleation behavior and interfacial chemistry of room temperature sodium-sulfur batteries

Room temperature sodium-sulfur (RT Na-S) batteries are considered as advanced energy storage technology due to their low cost and high theoretical energy density. However, challenges such as the growth of sodium dendrite and dissolution of sodium polysulfides significantly hinder the electrochemical performance. Herein, we developed a propylene carbonate (PC)-based electrolyte with Methyl 2-Fluoroisobutyrate (MFB) as an additive. The ester group in the MFB additive is capable of participating in and reconfiguring the coordination of their Na+ solvated structures, thereby lowering the desolvation barrier and regulating the Na anode’s interfacial reaction and nucleation behavior. The polar C−F bond at the other end helps to reduce the lowest unoccupied molecular orbital (LUMO) energy of the MFB additive, enabling the preferential decomposition of MFB to form the F-rich inorganic phase strong polar solid electrolyte interphase (SEI), contributing to the inhibition of Na dendrite growth, the accumulation of dead Na. In addition, NaF-riched cathode electrolyte interphase (CEI) was also observed on sulfur-based cathode, which can effectively inhibited the shuttle effect. Consequently, the developed RT Na-S battery exhibit excellent electrochemical performance.

Boron Surface Treatment of Li7La3Zr2O12 Enabling Solid Composite Electrolytes for Li-metal Battery Applications.

Despite being promoted as a superior Li-ion conductor, lithium lanthanum zirconium oxide (LLZO) still suffers from a number of shortcomings when employed as an active ceramic filler in composite polymer-ceramic solid electrolytes for rechargeable all-solid-state lithium metal batteries. One of the main limitations is the detrimental presence of Li2CO3 on the surface of LLZO particles, restricting Li-ion transport at the polymer-ceramic interfaces. In this work, a facile way to improve this interface is presented, by purposely engineering the LLZO particle surfaces for better compatibility with a PEO:LiTFSI solid polymer electrolyte matrix. It is shown that an surface treatment based on immersing LLZO particles in a boric acid solution can improve the LLZO surface chemistry, resulting in an enhancement in the ionic conductivity and cation transference number of the CPE with 20 wt.% of boron-treated LLZO particles compared to the analogous CPE with non-treated LLZO. Ultimately, an improved cycling performance and stability in Li // LiFePO4 cells was also demonstrated for the modified material.

Surface Chemistry Induced IgG Unfolding and Modulation of Immune Responses.

Immunoglobulin G (IgG) comprises a significant portion of the protein corona that forms on biomaterial surfaces and holds a pivotal role in modulating host immune responses. To shed light on the important relationship between biomaterial surface functionality, IgG adsorption, and innate immune responses, we prepared, using plasma deposition, four surface coatings with specific chemistries, wettability, and charge. We found that nitrogen-containing coatings such as these deposited from allylamine (AM) and 2-methyl-2-oxazoline (POX) cause the greatest IgG unfolding, while hydrophilic acrylic acid (AC) surfaces allowed for the retention of the protein structure. Structural changes in IgG significantly modulated macrophage attachment, migration, polarization, and the expression of pro- and anti-inflammatory cytokines. Unfolded IgG on the POX and AM surfaces enhanced macrophage attachment, migration, extracellular trap release, and pro-inflammatory factors production such as IL-6 and TNF-α. Retention of IgG structure on the AC surface downregulated inflammatory responses. The findings of this study demonstrate that the retention of protein structure is an essential factor that must be taken into consideration when designing biomaterial surfaces. Our study indicates that using hydrophilic surface coatings could be a promising strategy for designing immune-modulatory biomaterials for clinical applications.

Eco-friendly iron extraction from fe-containing copper smelting slag via reduction roasting with coal and magnetic separation: Experimental and mechanism insights

Copper smelting slag (CSS) is a byproduct produced during the thermal smelting of copper and poses a considerable environmental challenge, particularly in China, where its accumulated volume surpasses 1.8 billion tons. This study utilized the response surface method (RSM) to optimize experimental procedures and reduce costs, the results showed that the effects of each factor on iron recovery were in the following order: roasting temperature > roasting time > coke dosage. The optimized iron recovery of iron extraction from CSS by Magnetization-roasting reached 78.87 %, while the actual iron recovery was 78.84 %. The relative error is very small, indicating that the model is effective. Conducted the thermodynamic computational analysis to understand the migration of metal phases in CSS, employed XPS analysis to identify valence changes in key elements, and the clever combination of restricted reduction kinetics and SEM-EDS analysis shows that the reduction reaction of CSS is mainly controlled by interfacial chemistry and carbon gasification at low temperatures. By processing CSS, the study successfully produced environmentally friendly iron that can be recycled, offering a sustainable solution for managing toxic waste from copper production.

Dissolution of EAF slag minerals in aqueous media: Effects of sonication on brownmillerite and gehlenite

The accumulation of electric arc furnace slag (EAFS) in landfills has been causing severe environmental problems. This study examines the dissolution properties of EAFS minerals, including brownmillerite and gehlenite, essential for their possible use in resource recovery. An investigation was conducted to compare the effects of sonication and stirring on mineral dissolution while also assessing the usage of citrate as a complexing agent for gehlenite. Synthetic brownmillerite and gehlenite minerals were dissolved in aqueous solutions at room temperature using a 1:100 g/ml ratio. The dissolved elements were measured using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES), while zeta potential and X-ray Photoelectron Spectroscopy (XPS) were used to assess changes in surface chemistry. Brownmillerite had significant dissolution extents, with Al and Ca dissolving up to 16 % and 8 %, respectively, in contrast to gehlenite, which dissolved less than 2 % under similar conditions. Sonication significantly increased the dissolution of brownmillerite by up to 100 %, although its impact on gehlenite dissolution varied depending on the duration of time. Besides, adding citrate enhanced the leaching of Al and Ca from gehlenite by facilitating complexation. XPS data demonstrated differences in elemental ratios on brownmillerite and gehlenite surfaces affected by the method used and the presence of citrate. Lastly, the dissolution extents of Al and Ca from EAFS were up to 12 %, depending on time and mixing method, with a preference for sonication over stirring. In conclusion, this study showed that minerals in EAFS have distinct dissolution characteristics, and sonication and citrate can considerably enhance dissolution.

Catalytic Decomposition of Residual Hydrogen Peroxide in N-Methylmorpholine-N-oxide by Heteroatom Doping Modified Activated Carbon

N-methyloxymoroline-N-oxide (NMMO) has been used in large quantities for the production of new solvent-treated cellulose. But, excess H2O2 used in the synthesis of NMMO from N-methylmorpholine (NMM) can adversely affect the quality of the product. This study introduces a novel approach using nitrogen and sulfur co-doped activated carbon (N,S co-doped AC) to catalyze the decomposition of residual H2O2 in NMMO products. Characterization techniques including N2 adsorption/desorption, Raman, TEM, FT-IR, and XPS were used to study the surface properties and chemistry of activated carbon doped with heteroatoms. The results revealed that AC800NS800 (800 is the calcinate temperature, NS is denoted by the co-doped of N and S) exhibited superior catalytic performance for H2O2 decomposition compared to singly doped activated carbons. Notably, over 95% of H2O2 in NMMO was decomposed, which the catalytic efficiency of AC800NS800 is no significant loss after ten times reuse. The exceptional catalytic activity of AC800NS800 is attributed to the presence of various functional groups on the surface (graphitic carbon, graphitic nitrogen, and pyrrole nitrogen). EPR tests identified HO• and O2•− as the primary reactive species in the H2O2 decomposition process. This study provides valuable insights into the catalytic decomposition of H2O2 in NMMO solutions and offers a significant reference for the production of high-quality NMMO.

From cornfield to catalyst support: Eco-friendly synthesis of Cu/CuO nanoparticles, immobilization on the waste corn husk fibers, photocatalytic exploration and bioactivity evaluation

This study presents an innovative approach to eco-friendly synthesis and utilization of copper nanoparticles (CuNPs) for photocatalytic applications, employing waste corn husk fibers as sustainable catalyst support. The synthesis of CuNPs was achieved through a green synthesis method utilizing myrtle extract. Subsequently, the remarkable photocatalytic activity of the CuNPs explored (76% removal efficiency of Crystal Violet), showcased their potential in environmental remediation applications. Furthermore, the immobilization of CuNPs onto waste corn husk fibers was investigated, aiming to develop a novel composite material with enhanced catalytic performance. A distinctive approach was introduced by immobilizing CuNPs onto fibers derived from corn husks, and waste biomass material, leading to a significant enhancement in photocatalytic efficiency, surpassing 95.1%. Furthermore, bioactivity evaluation studies revealed the significant antioxidant, antidiabetic, DNA fragmentation, cell viability, antibiofilm and antimicrobial properties of CuNPs. The antioxidant ability was determined at 100 mg/L as 87.12%. The most powerful antimicrobial activity of CuNP was found as a MIC value of 8 mg/L against E. faecalis. The cell viability inhibition of CuNP was 90.05% at 20 mg/L. CuNP exhibited biofilm inhibition activity at different concentrations. The antibiofilm ability was investigated against Staphylococcus aureus compared to Pseudomonas aureginosa. While the DNA cleavage activity of CuNP observed double-strand breaks at 50 and 100 mg, complete fragmentation occurred at 200 mg concentrations. The bioactivity of the synthesized CuNPs shed light on their potential biomedical applications. The synthesized CuNPs are characterized using various analytical techniques to elucidate their structural and morphological properties. Fourier-transform infrared (FTIR) analysis provided insights into the chemical composition and surface properties of the synthesized materials. EDS analysis confirmed their successful integration into waste corn husk fibers. Overall, this interdisciplinary study highlights the potential of CuNPs immobilized on waste corn husk fibers for addressing environmental pollution, advancing sustainable technologies and paving the way for the development of efficient catalysts with diverse functionalities.

Characterization and comparability study of a series of novel fluorinated polyacrylates with a rigid cyclohexane mesogenic core

Surface reconstruction has always been a pain point in the study of short-chain perfluoroalkyl acrylate polymers, and how to maintain the balance between environmental protection and good performance is the key issue. We exploited the high efficiency and selectivity of the reaction between the isophorone di-isocyanate group and the hydroxyl group, and the rigid cyclohexane structure contained in their molecule to efficiently prepare a series of novel fluoro acrylate monomers (IFAM) containing rigid cyclohexane as mesogenic core and their homopolymers (PIFAM) with different lengths of short-chain perfluoroalkyl side chains. Their structures, liquid crystal behavior, thermal properties, surface chemical compositions, surface morphologies, and hydrophobicity were characterized and comparatively studied by FTIR, NMR, XRD, POM, DSC, TGA, XPS, AFM, and static/dynamic contact angle tester and dodecafluoroheptyl methacrylate (DFMA) and its homopolymer as a contrast. The results demonstrated that both the synthesized monomers and homopolymers possessed the expected chemical structures with thermotropic liquid crystalline behavior. Furthermore, the thermal stability and hydrophobicity of the polymers increased with the extension of the fluorocarbon chain length. The incorporation of the mesocrystalline motif and appropriate length of fluoroalkyl tails in the PIFAM polymers would enhance hydrophobic stability, as it promoted the crystallinity of the side chains and limited the structural rearrangement of the fluorocarbon chains. This study offers a straightforward method for synthesizing fluoro acrylate polymers with stable surface properties, highlighting their potential application in hydrophobic coatings.

Zincophilic Sites Enriched Hydrogen-bonded Organic Framework as Multifunctional Regulating Interfacial Layers for Stable Zinc Metal Batteries.

To construct an efficient regulating layer for Zn anodes that can simultaneously address the issues of dendritic growth and side reactions is highly demanded for stable zinc metal batteries (ZMBs). Herein, we fabricate a hydrogen-bonded organic framework (HOF) enriched with zincophilic sites as a multifunctional layer to regulate Zn anodes with controlled spatial ion flux and stable interfacial chemistry (MA-BTA@Zn). The framework with abundant H-bonds helps capture H2O and remove the solvated shells on [Zn(H2O)6]2+, leading to suppressed side reactions. The HOF layer also helps form electrolyte-philic surfaces and expose Zn (002) crystal planes which benefit for rapid conduction and uniform deposition of Zn2+, and weakened sides reactions. Additionally, the electrochemically active zincophilic sites (C=O, -NH2 and triazine groups) favor the targeted guidance and penetration of Zn2+ and provide advantageous sites for uniform Zn deposition. High Young's modulus of the HOF layer further contributes to a high interfacial flexibility and stability against Zn plating-associated stress. The MA-BTA@Zn symmetric cells thereby obtain a substantially extended battery life over 1000 h at 4 mA cm-2. The MA-BTA@Zn||Cu half-cell demonstrates a highly reversible Zn stripping/plating process over 1500 cycles with impressive average Coulombic efficiency (CE) of 99.5% at 10 mA cm-2.

Click-Chemistry-Enabled Functionalization of Cellulose Nanocrystals with Single-Stranded DNA for Directed Assembly.

Controlling the self-assembly of cellulose nanocrystals (CNCs) requires precise control over their surface chemistry for the directed assembly of advanced nanocomposites with tailored mechanical, thermal, and optical properties. In this work, in contrast to traditional chemistries, we conducted highly selective click-chemistry functionalization of cellulose nanocrystals with complementary DNA strands via a three-step hybridization-guided process. By grafting terminally functionalized oligonucleotides through copper-free click chemistry, we successfully facilitated the assembly of brushlike DNA-modified CNCs into bundled nanostructures with distinct chiral optical dichroism in thin films. The complexation behavior of grafted DNA chains during the evaporation-driven formation of ultrathin films demonstrates the potential for mediating chiral interactions between the DNA-branched nanocrystals and their assembly into chiral bundles. Furthermore, we discuss the future directions and challenges that include new avenues for the development of functional, responsive, and bioderived nanostructures capable of dynamic reconfiguration via selective complexation, further surface modification strategies, mitigating diverse CNC aggregation, and exploring environmental conditions for the CNC-DNA assembly.

Trace‐amount of Water as An Electrolyte Additive for Sodium Metal Electrode

The high reactivity of water toward Na metal has raised a concern about keeping the electrolytes extra‐dried. In this work, changes in water concentration in electrolytes (with and without fluoroethylene carbonate) show changes in overpotential and the surface chemistry of Na electrodes. In a symmetric cell test, the cell with pristine electrolyte (1M NaClO4 in ethylene carbonate:propylene carbonate) sustained only 22 cycles before reaching the safety limit (5 V) at 1 mA cm‐2. Meanwhile, controlling the water content (40 ppm) extended the cell’s life by 3.5 times. In fluoroethylene‐carbonate‐containing electrolytes, the optimized water concentration (40 ppm) gave the minimum overpotential (12 mV) after 170 cycles. Ex situ X‐ray photoemission spectroscopy showed that water hydrolyzed fluoroethylene carbonate, which changed the Na electrode’s surface chemistry. The appropriate amount of product (NaF) stabilized the electrodes’ surfaces. Electrical impedance spectroscopy showed that the controlled traces amount of water (40 ppm) always gave the minimum values for resistances. For the pristine electrolytes, the resistances attributed to the charge‐transfer process and the solid‐electrolyte interface layer increased 51 times (from 45 Ω to 2290 Ω) after cycling. Meanwhile, for the optimized sample, the resistances remarkably decreased by 93% (from 264 Ω to 19 Ω) after cycling.

Report on Reiwa 6th Annual Meeting of Kyushu Branch of The Japan Society of Vacuum and Surface Science

Report on Reiwa 6th Annual Meeting of Kyushu Branch of The Japan Society of Vacuum and Surface Science