Anodic Kinetics Research Articles

Quantitative pre-lithiation modulation of aluminum foil anode kinetics enables high rate and stable cycling of high-loading all-solid-state batteries

Aluminum (Al) foil holds great promise as a pure alloy anode for all-solid-state batteries (ASSBs) due to its suitable potential, high theoretical capacity, and excellent electronic conductivity. However, it remains challenging to achieve high reversibility and stability of the Al foil anode for ASSBs. Herein, we investigate the morphological and lithium (Li) kinetics evolutions of the Al foil anode paired with sulfide solid-state electrolyte (SSE). We identify that the significant reversible capacity loss stems from diminished Li kinetics at low Li contents (LixAl, 0 < x < 0.5), where the accumulation of pores and pure delithiated Al phase obstructs Li diffusion, increasing interfacial resistance and overpotential. Conversely, the Al foil anode with high Li contents (LixAl, 0.5 < x < 1) demonstrates reversible structures and rapid Li kinetics. Through precise pre-lithiation control, ASSBs with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes exhibit outstanding rate capabilities and cycling stability, achieving over 4,000 cycles with 82.1 % capacity retention at 5C and demonstrating long-term cycling over 1,000 cycles with nearly 100 % capacity retention at ultra-high loadings. This work offers a viable strategy for advancing practical-level ASSBs with enhanced performance and longevity, contributing valuable insights to future battery technology.

Blooming microflowers: Shaping TiO2 nanostructures via anodization in metal chloride-based electrolytes

TiO2 microflowers, consisting of nanotubes, were generated via potentiostatic anodization in fluoride-free electrolytes infused with metal chlorides. Anodizing titanium foil at 15 V for 10 min in electrolytes containing 0.1 M of FeCl3·6H2O, CrCl3·6H2O, FeCl2·4H2O, and CuCl2·2H2O yielded nanotubes with outer diameters of approximately 30 nm, 45 nm, 50 nm, and 60 nm, respectively. The introduction of metal chloride to the electrolyte significantly altered the anodization kinetics, facilitating the growth of TiO2 microflowers. These structures consist of nanotube bundles that are of few microns in length with tunable diameters, achieved rapidly within the anodization timeframe. Microflowers formed in FeCl3·6H2O electrolyte feature high aspect ratio TiO2 nanotube bundles with smaller diameters and higher nucleation density, whereas those developed in CrCl3·6H2O, FeCl2·4H2O, and CuCl2·2H2O electrolytes exhibit less preferable morphology.

Enhanced performance of quasi-solid-state silicon-air batteries through light-assisted anodic reactions

Silicon-air batteries (SABs) offer a promising energy storage solution due to their high theoretical energy density, cost-effectiveness, and environmental friendliness. However, practical applications are hindered by limitations in maximum discharge current density and discharge voltage, stemming from intrinsic electrochemical properties of the silicon (Si) anode and surface oxidation kinetics. This study addressed the low maximum discharge current density of SABs by leveraging the Si semiconductor properties and employing a light-assisted strategy. Introducing light to the silicon anode generates photogenerated electron-hole pairs. Furthermore, introducing light to the Si anode allowed for the generation of photogenerated electron-hole pairs. The resulting holes reacted with OH- ions to form hydroxyl radical (OH), which efficiently oxidized the Si surface, thereby facilitating electrochemical reactions. This enhancement increased the anodic reaction kinetics, thereby enhancing the maximum discharge current density of SABs. Furthermore, through this strategy, light-assisted SABs exhibited significant performance improvements: under 1 sun illumination, maximum discharge current density increased by 50.0 %, discharge voltage by 10.0 %, and power density by 45.0 %. Under 3 suns illuminations, these metrics improved further, with maximum discharge current density increasing by 87.5 %, discharge voltage by 20 %, and power density by 200 %. Additionally, quasi-solid-state SABs (QSSSABs) according to this strategy exhibited versatility across various application scenarios, thereby significantly expanding the practical potential of SABs technology.

Environmentally Assisted Cracking of Duplex and Lean Duplex Stainless Steel Reinforcements in Alkaline Medium Contaminated with Chlorides

Herein, the corrosion performance of different stainless steel (SS) reinforcing bar grades in alkaline solution is presented, including UNS S32205 duplex stainless steel (DSS), UNS S32304 and UNS S32001 lean DDS (LDSS). The electrochemical dissolution kinetics were studied by potentiodynamic polarization and the Tafel slope method. The environmentally assisted cracking (EAC) mechanisms of the different SS grades in the presence of Cl− were revealed with the slow strain rate test (SSRT). The higher activation of the anodic branch and the loss of toughness were related to the austenite-to-ferrite phase ratio. UNS S32205 DSS presented the slowest anodic dissolution kinetics, mainly due to the higher austenite content compared to the other LDSS; however, it suffered a more severe EAC than the UNS S32304 LDSS. In the case of UNS S32001 LDSS, even while having the lowest Ni content (i.e., large ferrite α-phase ratio), it experienced the least decrease in elongation as well as low anodic dissolution kinetics for Cl− contents up to 8 wt.%, where the Cl− threshold was reached.

In situ heating-induced loading of anion-rich vacancy Mo–Fe1-xS nanoparticles on mesoporous carbon for high-performance sodium-ion batteries

Inspiriting the kinetics of transition metal sulfide-based anodes is key to optimizing rate performance and cycling stability. To this end, the controllable anion vacancy and large specific surface area are considered as powerful means to improve the performance of sodium-ion batteries due to their unique physical and chemical properties and convenient transport paths. Hence, we have generated Fe3+/MoO42−@cystine nanosheets by solvothermal reaction with iron molybdate nanosheets using cysteine as a sulfur and carbon source. in situ environmental transmission electron microscopy demonstrates that the Fe3+/MoO42−@cystine nanosheets calcined under a vacuum state undergo significant structural evolution, consequentially, the decomposition and carbonization of cystine induces the generation of mesoporous structures with increasing temperature. In the half-cell, Mo–Fe1-xS@mesoporous nitrogen doped carbon-600 showed excellent rate capability at current densities of 0.1–5 A g−1, as well as excellent cycling performance (428.9 mAh g−1 at 2.0 A g-1 after 800 cycles). Mesoporous nitrogen doped carbon and sulfur vacancies induced enhanced conductivity, fast ionic transfer and structural stability, resulting in excellent electrochemical performance of Mo–Fe1-xS@mesoporous nitrogen doped carbon under calcination at 600 °C (Mo–Fe1-xS@MCN-600).

A Solid‐Solution with Asymmetric Ni‐O‐Cr Sites for Boosting Protonation toward Anodic Oxidation

AbstractReplacing the slow protonation process of oxygen evolution reaction (OER) with the fast protonation of alcohol electro‐oxidation can decrease the driving potentials, thus improving overall efficiency of electrochemical devices. However, the formation of effective catalytic sites for alcohol oxidation remains challenging in accelerating protonation to inhibit metal leaching and improve catalyst stability. Herein, asymmetric Ni‐O‐Cr sites are constructed by alloying Cr into the NiO matrix to optimize coordination environments, showing significantly enhanced stability during alcohol electro‐oxidation. The asymmetric Ni‐O‐Cr can maintain constant valence states of Cr and Ni during alcohol oxidation, efficiently suppressing metal dissolution even at high oxidation potentials. In situ electrochemical characterizations combined with theoretical calculations indicate that asymmetric Ni‐O‐Cr can improve adsorption and activation of OH* and alcohol molecules compared to pure NiO, thus increasing anodic kinetics. The theoretical results also indicate that the smaller gap of Ni 3d‐O 2p in asymmetric Ni‐O‐Cr strengthens charge transfer, leading to fast protonation of catalytic sites with enhanced stability. This work gives insights into boosting anodic protonation using asymmetric sites‐enriched solid‐solution electrocatalysts.

Enhanced 1,2-dichloroethane removal using g-C3N4/Blue TiO2 nanotube array photoanode in microbial photoelectrochemical cells

The compound 1,2-dichloroethane (1,2-DCA), a persistent and ubiquitous pollutant, is often found in groundwater and can strongly affect the ecological environment. However, the extreme bio-impedance of C–Cl bonds means that a high energy input is needed to drive biological dechlorination. Biotechnology techniques based on microbial photoelectrochemical cell (MPEC) could potentially convert solar energy into electricity and significantly reduce the external energy inputs currently needed to treat 1,2-DCA. However, low electricity-generating efficiency at the anode and sluggish bioreaction kinetics at the cathode limit the application of MPEC. In this study, a g-C3N4/Blue TiO2-NTA photoanode was fabricated and incorporated into an MPEC for 1,2-DCA removal. Optimal performance was achieved when Blue TiO2 nanotube arrays (Blue TiO2-NTA) were loaded with graphitic carbon nitride (g-C3N4) 10 times. The photocurrent density of the g-C3N4/Blue TiO2-NTA composite electrode was 2.48-fold higher than that of the pure Blue TiO2-NTA electrode under light irradiation. Furthermore, the MPEC equipped with g-C3N4/Blue TiO2-NTA improved 1,2-DCA removal efficiency by 45.21% compared to the Blue TiO2-NTA alone, which is comparable to that of a microbial electrolysis cell. In the modified MPEC, the current efficiency reached 69.07% when the light intensity was 150 mW cm−2 and the 1,2-DCA concentration was 4.4 mM. The excellent performance of the novel MPEC was attributed to the efficient direct electron transfer process and the abundant dechlorinators and electroactive bacteria. These results provide a sustainable and cost-effective strategy to improve 1,2-DCA treatment using a biocathode driven by a photoanode.

The anodic dissolution kinetics of Mg alloys in water based on ab initio molecular dynamics simulations

AbstractThe corrosion susceptibility of magnesium (Mg) alloys presents a significant challenge for their broad application. Although there have been extensive experimental and theoretical investigations, the corrosion mechanisms of Mg alloys are still unclear, especially the anodic dissolution process. Here, a thorough theoretical investigation based on ab initio molecular dynamics and metadynamics simulations has been conducted to clarify the underlying corrosion mechanism of Mg anode and propose effective strategies for enhancing corrosion resistance. Through comprehensive analyses of interfacial structures and equilibrium potentials for Mg(0001)/H2O interface models with different water thicknesses, the Mg(0001)/72 H2O model is identified to be reasonable with −2.17 V vs. standard hydrogen electrode equilibrium potential. In addition, utilizing metadynamics, the free energy barrier for Mg dissolution is calculated to be 0.835 eV, enabling the theoretical determination of anodic polarization curves for pure Mg that aligns well with experimental data. Based on the Mg(0001)/72 H2O model, we further explore the effects of various alloying elements on anodic corrosion resistance, among which Al and Mn alloying elements are found to enhance corrosion resistance of Mg. This study provides valuable atomic‐scale insights into the corrosion mechanism of magnesium alloys, offering theoretical guidance for developing novel corrosion‐resistant Mg alloys.

Design of dual carbon encapsulated porous micron silicon composite with compact surface for enhanced reaction kinetics of lithium-ion battery anodes

Developing high-performance composites with fast charging and superior cycle life is paramount for lithium-ion batteries (LIBs). Herein, we synthesized a double-shell carbon-coated porous structure composite with a compact surface (P-Si@rGO@C) using low-cost commercial micron-sized silicon (Si) instead of nanoscale silicon. Results reveal that the unique P-Si@rGO@C features high adaptability to volume expansion, accelerates electron/ion transmission rate, and forms a stable solid electrolyte interphase (SEI) film. This phenomenon arises from the synergistic effect of abundant internal voids and an external double-layer carbon shell with a dense surface. Specifically, the P-Si@rGO@C anode exhibits a high initial coulombic efficiency (ICE) (88.0 %), impressive rate-capability (612.1 mAh/g at 2C), and exceptional long-term cyclability (972.2 mAh/g over 500 cycles at 0.5C). Further kinetic studies elucidate the diffusion-capacitance hybrid energy storage mechanism and reveal an improved Li+ diffusion coefficient (from 3.47 × 10-11 to 2.85 × 10-9 cm2 s-1). Ex-situ characterization confirms the crystal phase change of micron-sized Si and the formation of a stable LiF-rich SEI. Theoretical calculations support these findings by demonstrating an enhancement in the adsorption ability of Si to Li+ (from -0.89 to -0.97 eV) and a reduction in the energy migration barrier (from 0.35 to 0.18 eV). Additionally, practical LixSi powder is shown to increase the ICE of full cells from 67.4 % to 87.9 %. Furthermore, a pouch cell utilizing the prelithiated P-Si@rGO@C anode paired with LiNi1/3Co1/3Mn1/3O2 (NCM111) cathode delivers a high initial reversible capacity of 7.2 mAh and 76.8 % capacity retention after 100 cycles. This work provides insights into the application of commercial silicon-aluminum alloy powder in the anode of high-energy LIBs.

High-Entropy Engineering of Cubic SiP with Metallic Conductivity for Fast and Durable Li-Ion Batteries.

A cost-effective, scalable ball milling process is employed to synthesize the InGeSiP3 compound with a cubic ZnS structure, aiming to address the sluggish reaction kinetics of Si-based anodes for Lithium-ion batteries. Experimental measurements and first-principles calculations confirm that the synthesized InGeSiP3 exhibits significantly higher electronic conductivity, larger Li-ion diffusivity, and greater tolerance to volume change than its parent phases InGe (or Si)P2 or In (or Ge, or Si)P. These improvements stem from its elevated configurational entropy. Multiple characterizations validate that InGeSiP3 undergoes a reversible Li-storage mechanism that involves intercalation, followed by conversion and alloy reactions, resulting in a reversible capacity of 1733mAhg-1 with an initial Coulombic efficiency of 90%. Moreover, the InGeSiP3-based electrodes exhibit exceptional cycling stability, retaining an 1121mAhg-1 capacity with a retention rate of ≈87% after 1500 cycles at 2000mAg-1 and remarkable high-rate capability, achieving 882mAhg-1 at 10 000mAg-1. Inspired by the distinctive characteristic of high entropy, the synthesis is extended to high entropy GaCu (or Zn)InGeSiP5, CuZnInGeSiP5, GaCuZnInGeSiP6, InGeSiP2S (or Se), and InGeSiPSSe. This endeavor overcomes the immiscibility of different metals and non-metals, paving the way for the electrochemical energy storage application of high-entropy silicon-phosphides.

Li5.5PS4.5Cl1.5-Based All-Solid-State Battery with a Silver Nanoparticle-Modified Graphite Anode for Improved Resistance to Overcharging and Increased Energy Density.

All-solid-state lithium batteries (ASSLBs) are attracting tremendous attention due to their improved safety and higher energy density. However, the use of a metallic lithium anode poses a major challenge due to its low stability and processability. Instead, the graphite anode exhibits high reversibility for the insertion/deinsertion of lithium ions, giving ASSLBs excellent cyclic stability but a lower energy density. To increase the energy density of ASSLBs with the graphite anode, it is necessary to lower the negative/positive (N/P) capacity ratio and to increase the charging voltage. These strategies bring new challenges to lithium metal plating and dendrite growth. Here, a nano-Ag-modified graphite composite electrode (Ag@Gr) is developed to overcome these shortcomings for Li5.5PS4.5Cl1.5-based ASSLBs. The Ag@Gr composite exhibits a strong ability to inhibit lithium metal plating and fast lithium-ion transport kinetics. Ag nanoparticles can accommodate excess Li, and the as-obtained Li-Ag alloy enhances the kinetics of the composite electrode. The ASSLB with the Li(Ni0.8Co0.1Mn0.1)O2 cathode and Ag@Gr anode achieves an energy density of 349 W h kg-1. The full cell using Ag@Gr with an N/P ratio of 0.6 also highlights the rate performance. This work provides a simple and effective method to regulate the charge transport kinetics of graphite anodes and improve the cyclic performance and energy density of ASSLBs.

Microcell and macrocell corrosion kinetics of steel bars in reinforced concrete slabs subjected to alternate wet and dry environments

Electrochemical kinetics of steel bar corrosion in concrete is of complex nature, especially when it is subjected to alternate wet and dry environments with changes in conditions of steel-concrete interface and rust properties. In this paper, a quantitative electrochemical mechanism was proposed based on thermodynamics and anodic polarisation kinetics to account for variations of microcell and macrocell current densities in reinforced concrete (RC) slabs subjected to periodic wetting and drying cycles. Effects of environmental conditions on corrosion process were incorporated into anodic Tafel slope through three quantifiable parameters, namely, corrosion potential, linear polarisation resistance and ferrous ion concentration at the steel bar surface. A numerical model was established based on the proposed mechanism to quantify microcell and macrocell current densities. An experimental programme of two RC slabs with multiple steel bars arranged at different layers was conducted to verify the numerical model. It shows that the model could reasonably predict variations of both microcell and macrocell corrosion under different wet and dry environments. When concrete was moistened, current density was substantially increased compared to that in dry concrete. Macrocell contribution from uncorroded steel bars at different layers was more significant than microcell corrosion on the corroded bar itself, especially in wet environments.

Resolving the tradeoff between energy storage capacity and charge transfer kinetics of sulfur-doped carbon anodes for potassium ion batteries by pre-oxidation-anchored sulfurization

Sulfur-heteroatom doping is an effective approach to improve the capacity of carbon anodes for potassium-ion batteries due to the reversible K+-sulfur reaction. However, the random sulfur doping induces unresolved tradeoff between capacity and kinetics, which results from the fundamental difficulty in controllable sulfur incorporation using traditional approaches where breaking robust carbon-containing bonds is necessary. Herein, a pre-oxidation-anchored sulfurization approach is proposed to realize site-controlled and content-adjustable sulfur doping, demonstrating the optimum sulfur content of 9.8 at.% in sulfur-doped hollow carbon sphere (S-HCS). Intentional pre-oxidation introduces easy-to-break C-O/C-O-C bond-included oxygen-containing functional groups serving as anchoring sites for substitution with sulfur atoms. Consequently, S-HCS-9.8 % achieves superior performance for K+ storage (406.1 mA h g–1 at 0.1 A g–1, 112.6 mA h g–1 at 5 A g–1 and 170 mA h g–1 after 2,000 cycles at 2 A g–1). The enhanced electrochemical performances are attributed to the largest interlayer spacing and highest disorder degree resulting from the thiophene-sulfur-dominated configuration at high sulfur content, which realizes high structure reversibility and stable solid-electrolyte-interface layer. This work provides new insights and guiding principles for the development of heteroatom-doped carbon anodes for next-generation high-performance energy storage applications.

Enhancing the oxygen evolution activity and stability of Pb anode in Mn2+-containing acidic solution by embedding MnCo2O4 particles

Due to the excellent activity and stability of MnCo2O4 toward the oxygen evolution reaction (OER) in acidic solution, a Pb–MnCo2O4 composite anode for zinc electrowinning was prepared by embedding dispersed MnCo2O4 particles into a Pb matrix in a powder metallurgy process. In this work, the phase structure, chemical composition, and morphology of the oxide layers formed on Pure-Pb and Pb–MnCo2O4 were analyzed by XRD, SEM, and EDS. Galvanostatic polorization, Tafel tests, and EIS measurements were performed to investigate the anodic potential variation and OER kinetics of the Pure-Pb and Pb–MnCo2O4 composite anodes. Compared with that on the Pure-Pb anode, the oxide layer on Pb–MnCo2O4 is thinner, more compact, and more stable in a 160 g L−1 H2SO4 solution containing 4 g L−1 Mn2+. Consequently, the Pb–MnCo2O4 composite anode exhibited a much lower anode slime production (8.7 mg) during 72 h of the simulated zinc electrowinning process. Despite the smaller surface area and lower PbO2 content of the oxide layer, the Pb–MnCo2O4 composite anode presented preferable OER kinetics with a lower OER charge transfer resistance (0.729 Ω cm2) and a smaller Tafel slope (90.74 mV dec−1), which contributed to a 70 mV reduction in the anodic potential compared with that of the Pure-Pb anode.

Balancing the Ion/Electron Transport of Graphite Anodes by a La-Doped TiNb2O7 Functional Coating for Fast-Charging Li-Ion Batteries.

A functional coating layer (FCL) is widely applied in fast-charging lithium-ion batteries to improve the sluggish Li+ transport kinetics of traditional graphite anodes. However, blindly increasing the Li+ conductivity for FCL reduces the overall electron conductivity of the anodes. Herein, we decoupled the effect of La-doping on TiNb2O7 (TNO) in terms of the phase evolution, Li+/electron transport, and lithiation behavior, and then proposed a promising La0.1TNO FCL with balanced Li+/electron transport for a fast-charging graphite anode. By optimizing the doping concentration of La, more holes are introduced into the TNO as electron carriers without causing lattice distortion, thus maintaining the fast Li+ diffusion channel in TNO. As a result, the graphite with La0.1TNO FCL delivers an excellent capacity of 220.2 mAh g-1 (96.3% retention) after 450 cycles at 3 C, nearly twice that of the unmodified one.

Simultaneously manipulating carbon coating layers and void structures in silicon/carbon anode materials via bifunctional templates for lithium-ion batteries

The carbon coating strategies, ameliorating structure instability and reaction kinetics of silicon anodes upon lithiation/delithiation, have been chronically plagued by an electrochemical contradiction between a high specific capacity from a high silicon content and a long cycle life from a high carbon content. Herein, the carbon coating layers and void structures for silicon/carbon composites were simultaneously manipulated through a precisely grown Al2O3 template, which induced a controllable polydopamine polymerization through its mild interfacial interaction with Tris-buffer solution and created abundant void spaces by its residual parts. Particularly, the as-optimized silicon/carbon composite with an ultrahigh silicon content of 89.3 wt% could demonstrate a large initial reversible capacity of 2583 mAh g−1 with an 82.1 % coulombic efficiency at 200 mA g−1, a remarkable cycling durability of 601 mAh g−1 after 990 cycles at 2000 mA g−1, and an excellent rate capability of 887 mAh g−1 at 4000 mA g−1. The uniform void structures could maintain the structural stability/integrity of silicon, boost reaction kinetics across electrode/electrolyte interfaces, and suppress the uncontrollable formation/evolution of solid electrolyte interphases upon cycling. This novel research on synchronously regulating carbon layers and void structures in silicon/carbon composites would enlighten a rational development of high-capacity and long-life silicon anodes.

Effect of Microstructure on Corrosion Behavior of Cold Sprayed Aluminum Alloy 5083

This paper investigates the effect of the microstructure on the corrosion behavior of cold sprayed (CS) AA5083 compared to its wrought counterpart. It has been shown that the microstructure of CS aluminum alloys, such as AA2024, AA6061, and AA7075, affects their corrosion behavior; however, investigations of the corrosion behavior of CS AA5083 with a direct comparison to wrought AA5083 have been limited. The microstructure and corrosion behavior of CS AA5083 were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), electron backscattered diffraction (EBSD), electrochemical and immersion tests, and ASTM G67. The CS process resulted in microstructural changes, such as the size and spatial distribution of intermetallic particles, grain size, and misorientation. The refined grain size and intermetallic particles along prior particle boundaries stimulated the initiation and propagation of localized corrosion. Electrochemical tests presented enhanced anodic kinetics with high pitting susceptibility, giving rise to extensive localized corrosion in CS AA5083. The ASTM G67 test demonstrated significantly higher mass loss for CS AA5083 compared to its wrought counterpart due to preferential attack within prior particle boundary regions in the CS microstructure. Possible mechanisms of intergranular corrosion (IGC) propagation at prior particle boundary regions have been discussed.

Defect-rich Pt-Ru metallic aerogels for highly efficient ethanol oxidation reaction

Direct ethanol fuel cells (DEFCs) are a new type of green and efficient energy conversion devices, but the slow anodic reaction kinetics limit their application. Herein, a series of Pt-Ru metallic aerogels (MAs) with controllable composition, rich surface defects, and large specific surface area were prepared for ethanol oxidation reaction (EOR) by freeze–thaw method. Pt6Ru MAs exhibit the highest mass activity (1.264 A mgPt−1) toward EOR among all the catalysts we have prepared, which is 2.0, 1.8, and 3.7 times higher than those of Pt MAs (0.632 A mgPt−1), the commercial Pt/C (0.696 A mgPt−1), Pt6Ru NPs (0.339 A mgPt−1). 1H nuclear magnetic resonance spectroscopy confirms that only acetic acid was the liquid product of Pt6Ru MAs during EOR catalysis. Furthermore, Pt6Ru MAs show little attenuation and satisfactory reactivation abilities in stability assessment, demonstrating their good stability. This proves that the introduction of Ru makes feasible adjustments to the electronic structure of Pt in MAs, improving the electrocatalysis activity of Pt6Ru MAs in EOR. Mechanistic investigations reveal that the optimal electronic structure is the intrinsic reason for the excellent EOR performance of Pt6Ru MAs. The findings open a new way to develop high-performance Pt-based materials electrocatalysts.

(Invited) On the Inhibition Mechanism of an Alkylammonium Nitrate Ionic Liquid Family on Al Alloys: Electrochemical and XPS/in Situ PM-IRRAS Studies

AA2024 are high strength Al alloys widely used in the aerospace industry due to their excellent strength to weight ratio. However, their high susceptibility to localised corrosion, caused by the presence of intermetallic particles embedded in the Al matrix, requires the use of chromate-based surface treatment formulations1. Several alternatives have been explored in the last decades, such as vanadates, chromium (III) based conversion coatings, rare-earth inhibitors or more recently, lithium containing conversion coatings2. However, these alternatives are often not versatile (cannot be transposed to all alloy systems) or are not as cost effective as chromates. Ionic liquids (ILs), usually defined as salts with a melting point below 100°C, can be considered as promising corrosion inhibitors due to their low vapour pressure, chemical and thermal stability3. In addition, they can exhibit versatile inhibition properties associated with the quasi-infinite possible anion-cation combinations3–5. In previous work, the effect of an alkylammonium nitrate IL family, namely ethylammonium nitrate (EAN), propylammonium nitrate (PAN), and butylammonium nitrate (BAN) as potential corrosion inhibitors for an AA2024-T6 Al alloy was investigated6. Electrochemical tests such as potentiodynamic polarisation and electrochemical impedance spectroscopy were performed to identify the effect of the anion and cation on the anodic and cathodic kinetics. Herein, surface analysis was performed to rationalise the electrochemical results, particularly on the reactivity of NO3 - and R-NH3 + on the Cu-rich intermetallic particles. To this end, electrospray ionisation of EAN, BAN and NaNO3 was realised on Cu. The effect of the IL concentration and cation chain length, using PM-IRRAS (polarisation modulation -infrared reflection adsorption spectroscopy) was used to investigate molecule orientation and surface-molecule bonding as a function of surface coverage; The results provided new insights on the inhibition mechanism of this IL family. O. Gharbi, S. Thomas, C. Smith, and N. Birbilis, Npj Mater Degrad, 2, 12 (2018) http://www.nature.com/articles/s41529-018-0034-5.A. Kosari et al., Corros Sci, 190, 109651 (2021) https://doi.org/10.1016/j.corsci.2021.109651.C. Verma, E. E. Ebenso, and M. A. Quraishi, J Mol Liq, 233, 403–414 (2017) http://dx.doi.org/10.1016/j.molliq.2017.02.111.J. Sun, P. C. Howlett, D. R. MacFarlane, J. Lin, and M. Forsyth, Electrochim Acta, 54, 254–260 (2008).N. V. Likhanova et al., Corros Sci, 52, 2088–2097 (2010) http://dx.doi.org/10.1016/j.corsci.2010.02.030.A. Z. Benbouzid et al., Corrosion Communications, 9, 57–64 (2023).

Constructing a Highly Robust Interface Film for Enhancing Rate Performance of Graphite Anode via a Novel Electrolyte Additive.

Solid electrolyte interphase (SEI) is regarded as a key factor to enable high power outputs of Lithium-ion batteries (LIBs). Herein, we demonstrate a modified electrolyte consisting of a novel electrolyte additive, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (FTMS) to construct a highly robust and stable SEI on a graphite anode for LIBs to enhance its rate performance. With 2% FTMS, the anode presents an improved capacity retention from 77.6 to 91.2% at 0.5 C after 100 cycles and an improved capacity from 86 to 229 mAh g-1 at 2 C. Experimental characterizations and theoretical calculations reveal that FTMS is preferentially absorbed and reduced on graphite to construct an interface chemistry with uniform fluoride-containing organic lithium salt and silicon-containing polymer, which exhibits high flexibility and conductivity and endows the SEI with high robustness and stability. This work provides an effective way to address the issue of slow lithium insertion/desertion kinetics of graphite anodes.