Anode Production Research Articles

Dual functionality of cathode microporous layers: Reducing hydrogen permeation and enhancing performance in proton exchange membrane water electrolyzers

Hydrogen permeation and cell performance are critical factors for the safe and efficient operation of proton exchange membrane (PEM) water electrolysis. In this study, the effects of a cathode microporous layer (MPL) on water transport, hydrogen permeation, and cell performance in a proton exchange membrane water electrolyzer (PEMWE) were investigated. Results reveal that adding an MPL between the catalyst layer (CL) and the porous transport layer (PTL) at the cathode reduces interfacial contact resistance by approximately 60 % under 400 N cm−2, leading to superior performance. The wettability of the MPL plays a crucial role in water transport and hydrogen permeation in PEMWEs. The hydrophobic MPL-P-CB4, which uses polytetrafluoroethylene (PTFE) as a binder with a carbon black (CB) loading of 4 mgCB cm−2, enhances the crossover of water and hydrogen from the cathode to the anode through back diffusion, exceeding the technical safety criterion of 2 vol% H2 in the anode product gas (50 % lower explosion limit) at 2.0 A cm−2. However, the hydrophilic MPL with Nafion ionomers as binders (MPL-N-CB4) facilitates efficient removal of water and hydrogen from the cathode CL to the cathode flow field via capillary pressure, resulting in only 0.2 vol% H2 in O2 at 2.0 A cm−2. Consequently, a hydrophilic MPL is optimal for achieving superior performance and low-hydrogen-crossover in a PEMWE cathode. This study provides valuable insights for designing the PTL/CL interface in next-generation PEMWE cathodes.

Cu-doped Ni3S2 electrocatalyst for glycerol oxidation coupling to promote hydrogen evolution reaction

Hydrogen energy is becoming increasingly important as a clean and efficient form of energy. Glycerol oxidation synergistic electrocatalytic hydrogen evolution technology is an electrochemical process that integrates anodic glycerol oxidation reaction (GOR) and cathodic hydrogen production. Compared with the oxygen evolution reaction (OER) required in the electrolysis of water for hydrogen production process, this technology can not only reduce the energy consumption of the whole reaction, but also obtain valuable by-products while producing hydrogen. In this study, we successfully prepared a copper-doped Ni3S2 (Cu-Ni3S2@NF) electrode material loaded on a nickel foam carrier by a two-stage hydrothermal synthesis method, and applied it to the bifunctional electrocatalytic reaction of GOR and hydrogen evolution reaction (HER). After a series of in-depth electrochemical performance tests, it was confirmed that 0.1Cu-Ni3S2@NF showed lower overpotential requirements when performing GOR and HER, requiring only 1.41 V relative to the reversible hydrogen electrode (RHE) to drive a current density of 100 mA cm−2 for GOR, and only 0.56 V vs. RHE to achieve the same current density for HER. Moreover, the electrode material still maintains good stability under long-term operation. Among them, the Faraday efficiency (FE) of glycerol oxidation to formate is more than 85 %, while the FE of HER is not less than 93 %.

Water Soluble Poly(amic acid) Binder for Anode Coating and High Temperature Processing

The advent of lithium batteries has been a cornerstone in the evolution of electric vehicle technology, offering a sustainable alternative to fossil fuels and transforming the transportation landscape. The integration of water-soluble binders in the scalable production of anodes significantly enhances the efficiency and sustainability of lithium battery manufacturing. Further advances in battery manufacturing require enhanced tolerance to high temperatures and increased mechanical robustness, especially for high-throughput roll-to-roll production process. In this study, we present a water-soluble poly(amic acid)-based binder, uniquely designed to facilitate aqueous coating processes and withstand high processing temperatures for anode manufacturing. This innovative binder demonstrates remarkable efficiency in securely binding active materials, such as graphite or silicon, ensuring their integrity and performance throughout the battery cycling process.

A Sustainable Recycling Approach to Regenerate Graphite from Industrially Sourced Failed Anodes

Recycling graphite from Li-ion battery (LIB) waste plays an important role in increasing the accessibility of graphite resources and sustainable recovery. This presentation describes our work to purify graphite from failed (i.e., out-of-specification) anodes in LIB manufacturing by focusing on the most common contaminant: copper, used as the current collector in LIB anodes.A new, three-step scalable and environmentally friendly approach was used to provide a cost-effective and sustainable method in industrial settings to recycle failed anodes during the early stages of battery manufacturing.The study aimed to understand the differences between new, battery-grade graphite and recycled graphite from anode production waste. In particular, focus was placed on the effect of metallic Cu residues on electrochemical performance. The efficiency of Cu removal from graphite was quantified by Microwave Plasma – Atomic Emission Spectroscopy (MP-AES) analysis of leachates. The following experimental parameters were studied to maximize Cu leaching efficiency: solid-to-liquid ratio, temperature, acid concentration, time and stirring speed.The surface morphology and elemental composition of leached and thermally treated purified graphite were analysed by Scanning Electron Microscopy – Energy Dispersive Spectroscopy (SEM-EDS) and Laser Induced Breakdown Spectroscopy (LIBS). The specific surface area and crystallographic parameters were measured by Braunauer–Emmett–Teller Analysis (BET) and X-Ray Diffraction (XRD), respectively. The electrochemical performance was evaluated by galvanostatic cycling with potential limitation versus Li+/Li. These five techniques were carried out on the solid residues after each stage of the regeneration procedure. The results were compared with battery-grade graphite to assess the effectiveness of our sustainable recycling approach to reuse graphite from failed anodes in LIBs.

Sub-minute carbonization of polymer/carbon nanotube films by microwave induction heating for ultrafast preparation of hard carbon anodes for sodium-ion batteries

Hard carbons (HCs) are excellent anode materials for sodium-ion batteries (SIBs). However, the carbonization and granulation of HC powders involve complex processes and require considerable energy. Here, we developed a facile method for manufacturing HC anodes for SIBs via a novel microwave induction heating (MIH) process for polymer/single-walled carbon nanotube (SWCNT) films. Numerical simulations solving electromagnetic field and heat transfer problems revealed the MIH mechanism; the electric current induced by the applied microwave enables direct Joule heating of the SWCNT networks in the composite film. Consequently, the composite films could be heated to the target temperatures (800–1400 °C) and free-standing HC/SWCNT anodes could be prepared by applying MIH for only 30 s. Comparative analyses confirmed that ultrafast MIH is a reliable technique for producing HC anodes and can replace conventional carbonization processes which require a high-temperature furnace. Moreover, the HC/SWCNT anodes prepared by the ultrafast MIH were successfully applied to the SIB full cells. Finally, the feasibility of MIH for scalable roll-to-roll production of HC anodes was verified through local heating tests using a circular sheet larger than a resonator.

Fabrication and optimization of bioelectrochemical system using tetracycline-degrading bacterial strains for antibiotic wastewater treatment

In this study, a microbial fuel cell was constructed using Raoultella sp. XY-1 to efficiently degrade tetracycline (TC) and assess the effectiveness of the electrochemical system. The degradation rate reached 83.2 ± 1.8 % during the 7-day period, in which the system contained 30 mg/L TC, and the degradation pathway and intermediates were identified. Low concentrations of TC enhanced anodic biofilm power production, while high concentrations of TC decreased the electrochemical activity of the biofilm, extracellular polymeric substances, and enzymatic activities associated with electron transfer. Introducing electrogenic bacteria improved power generation efficiency. A three-strain hybrid system was fabricated using Castellaniella sp. A3, Castellaniella sp. A5 and Raoultella sp. XY-1, leading to the enhanced TC degradation rate of 90.4 % and the increased maximum output voltage from 200 to 265 mV. This study presents a strategy utilizing tetracycline-degrading bacteria as bioanodes for TC removal, while incorporating electrogenic bacteria to enhance electricity generation.

Anodic Production and Characterization of Biomimetic Oxide Layers on Grade 4 Titanium for Medical Applications.

Biomaterials are the basis for the development of medicine because they allow safe contact with a living organism. The aim of this work was to produce innovative oxide layers with a microporous structure on the surface of commercially pure titanium Grade 4 (CpTi G4) and to characterize their properties as drug carriers. The anodization of the CpTi G4 subjected to mechanical grinding and electrochemical polishing was carried out in a solution of 1M ethylene glycol with the addition of 40 g of ammonium fluoride at a voltage of 20 V for 2, 18, 24, and 48 h at room temperature. It was found that the longer the anodization time, the greater the number of pores formed on the CpTi G4 surface as revealed using the FE-SEM method, and the greater the surface roughness determined in profilometric tests. As the anodizing time increases, the amount of the drug in the form of gentamicin sulfate incorporated into the resulting pores decreases. The most favorable drug release kinetics profile determined via UV-VIS absorption spectroscopy was found for the CpTi G4 anodized for 2 h.

In-Sn alloy extraction through novel process for recycling of spent ITO targets

The feasibility of utilizing spent indium tin oxide (s-ITO) as an inert anode for the recovery of s-ITO targets through the electro-deoxidation was investigated, which concurrently achieved the avoidance of molten salt pollution caused by graphite anodes and maximized the utilization of resources by using the same material as the anode and cathode. Various techniques including anodic polarization and Tafel polarization were employed to evaluate the corrosion resistance and electrochemical stability of s-ITO. XRD and XPS are used to analyze the phase and valence state of the anodic materials and products, respectively. The practicability of replacing graphite anodes with s-ITO anodes was discussed in detail under identical electrolytic conditions. When using s-ITO as the anode, the carbon content and oxygen content in the electrolytic product are 31 ppm and 57 ppm, respectively, which are lower than those of graphite as the anode. Moreover, based on the results of above investigations, a cathode and anode collaborative electrolytic device was devised to maximize the utilization of resources and recovery of high-value products. The findings indicate that s-ITO has good corrosion resistance when used as an inert anode.

Combined anodic and cathodic peroxide production in an undivided carbonate/bicarbonate electrolyte with 144% combined current efficiency

In recent years, the electrochemical synthesis of peroxides has attracted renewed interest as a potential environmentally friendly production compared to the established anthraquinone process. In addition, it is possible to produce the peroxides directly on site, eliminating the need for expensive and hazardous transportation and storage. Cathodic production of hydrogen peroxide from oxygen is already quite well developed. Anodic production from water, on the other hand, is still facing significant challenges, despite its historic pioneering role. In this manuscript we show that anodic and cathodic synthesis of peroxides can even be combined to achieve greater than 100% current efficiency (CE) due to the combined effect of both half-reactions. So far, similar devices have always employed different electrolytes for each, which necessitated the use of a membrane and posed contamination risk. However, herein we show that both half-reactions can also employ the same electrolyte. This enables even an undivided cell, omitting the need for the expensive membranes. Despite its simplicity, this setup yielded an outstanding performance with a combined CE of 144%.

Scalable Customization of Crystallographic Plane Controllable Lithium Metal Anodes for Ultralong-Lasting Lithium Metal Batteries.

A formidable challenge to achieve the practical applications of rechargeable lithium (Li) metal batteries (RLMBs) is to suppress the uncontrollable growth of Li dendrites. One of the most effective solutions is to fabricate Li metal anodes with specific crystal plane, but still lack of a simple and high-efficient approach. Herein, a facile and controllable way for the scalable customization of polished Li metal anodes with highly preferred (110) and (200) crystallographic orientation (donating as polished Li(110) and polished Li(200), respectively) by regulating the times of accumulative roll bonding, is reported. According to the inherent characteristics of polished Li(110)/Li(200), the influence of Li atomic structure on the electrochemical performance of RLMBs is deeply elucidated by combining theoretical calculations with relative experimental proofs. In particular, a polished Li(110) crystal plane is demonstrated to induce Li+ uniform deposition, promoting the formation of flat and dense Li deposits. Impressively, the polished Li(110)||LiFePO4 full cells exhibit unprecedented cycling stability with 10000 cycles at 10 C almost without capacity degradation, indicating the great potential application prospect of such textured Li metal. More valuably, this work provides an important reference for low-cost, continued, and large-scale production of Li metal anodes with highly preferred crystal orientation through roll-to-roll manufacturability.

L-arginine-etched nickel-silver electrocatalyst for low-potential hydrogen evolution

The oxidation of formaldehyde at low potentials to achieve anodic hydrogen production is a crucial focus of current research. Copper-based alloys are prominent electrocatalysts in these reactions but face long-term stability challenges and are susceptible to CO intermediate poisoning. A novel approach that utilizes L-arginine in the surface modification of nickel foam substrates has been developed, enabling the highly dispersed deposition of silver catalysts on the substrates as sub-nanometer particles. This modified electrocatalyst allows formaldehyde oxidation and water electrolysis at a minimal potential of 0.32 VRHE and bipolar hydrogen production with near 100% Faradaic efficiency. This surface modification of substrate material provides a new approach to the design of electrodes.

An experimentally validated model for anodic H2O2 production in alkaline water electrolysis and its implications for scaled-up operation

The anodic co-production of hydrogen peroxide (H2O2) during alkaline water electrolysis has gained interest as a sustainable alternative for anthraquinone oxidation. However, electrochemical H2O2 production is often studied with idealized laboratory setups to determine the H2O2 formation kinetics. In this work, we perform the reaction with industrially relevant operating principles using a flow cell with separately recirculating anolyte and catholyte. We then fit the data to an analytical model that we derive based on mole balances that accounts for anodic generation, anodic oxidation, and bulk disproportionation of H2O2, as well as electrolyte volumes and electrode surface area. We performed experiments at 100, 200, and 300 mA cm-2 to derive values for the reaction system. At 200 mA cm-2, we found a generation rate of 0.037 mmol min-1 cm-2 (FEH2O2 = 59%) and an anodic decomposition rate constant of 0.304 cm min-1, with a bulk disproportionation rate constant of 1.85 × 10-3 min-1. We successfully applied our model to two sources in literature to derive values for their systems as well. In all cases, the contribution of anodic oxidation of H2O2 was found to be the larger loss mechanism in comparison to bulk disproportionation. Using the analytical model, we show that decreasing the reservoir volume is a simple way to increase the H2O2 concentration over time. Further refinement of the model can be achieved through the use of mass transfer relationships based on electrolyzer geometries to describe the anodic oxidation of H2O2 in the mole balance equations.

Electrochemical cobalt oxidation in chloride media

The green transition, despite recent advances in cobalt-free battery technologies, is still highly dependent on the availability of critical cobalt-based materials. Consequently, there has been increasing interest towards the development of new methods that maximize critical metals recovery from industrial hydrometallurgical solutions. In the current study, direct anodic oxidation of cobalt species from cobalt chloride solutions was studied as one alternative future strategy for cobalt recovery. Electrochemical methods were used (cyclic voltammetry, potentiostatic anodic deposition) and the effect of pH, temperature, and the concentration of cobalt and chloride ions on cobalt precipitation were investigated. The increase of pH and temperature was shown to stabilize the electrochemical oxidation of cobalt, while a decrease in cobalt concentration had a negative effect on precipitation. Scanning Electron Microscope, Atomic Force Microscopy and X-ray Photoelectron Spectroscopy were exploited to evaluate the morphology, structure, and composition of obtained anodic product. Calculated for potentiostatic anodic deposition (at highest studied potential of 1300 mV vs. Ag/AgCl) nucleation mechanism shows that the rate of nucleation for oxygen-cobalt species is faster than the subsequent growth rate of nuclei (instantaneous mechanism). XPS results confirmed that mixed Co3O4/Co(OH)2/CoOOH precipitate could be obtained by optimized anodic potentiostatic deposition in the range from 900 to 1150 mV and pH from 3 to 6 at 60 °C.

Carbon structural evolution and interfacial reaction mechanism investigation of the green anode in kneading and baking via ReaxFF-MD and force-biased Monte Carlo

ABSTRACT Baking is the most costly and critical process in anode preparation, and the study from the microscopic scale is conducive to the optimisation of anode baking process. In this research, a hybrid simulation method of reactive force field molecular dynamics (ReaxFF-MD) and force-biased Monte Carlo (fbMC) was proposed to understand the interaction mechanism between coal tar pitch (CTP) and calcined petroleum coke (CPC) during kneading and baking processes, and to explore the optimal ratio of CTP from the molecular scale. Results showed that the CTP content of 14 wt.% was beneficial for anode production. The mechanism of anode coking behaviour at high temperatures was also analyzed. The carbonisation of CTP during high-temperature baking broke the carbon rings and formed straight chains, exposing active carbon atoms that can bond with the remaining layers. As the high-temperature simulation progresses, the carbon chains at the bonding sites became increasingly cyclized and aromatised, which made the layered structure of the baked block similar to that of graphite. The generation of various volatile hydrocarbons during the baking process was observed, namely CH4, C2H4, C2H2, C2H6, and C3H6. This work provides theoretical basis for process optimisation.

Nanodiamond Implanted Zinc Metal Anode for Long‐Life Aqueous Zinc Ion Batteries

AbstractThe practical application of aqueous zinc ion batteries is greatly hindered by the severe dendrite growth and side reactions on the Zn metal anode. To address these challenges, nanodiamond (ND) particles are implanted on the Zn foil surface by a straightforward mechanical rolling process, which serves as heterogeneous seeds, enhancing the cycling stability of Zn metal anode. ND particles with carboxyl groups facilitate the even distribution of electric fields and Zn2+ ions in their vicinity, which promotes the homogeneous deposition of Zn. Moreover, the excellent corrosion resistance of ND particles alleviates the side reactions of the electrode, thus effectively protecting the Zn metal anode in aqueous electrolyte. Benefited from these advantages, the ND@Zn anode shows over 4100 h reversible cycles in symmetric cells, and 99.7% Coulombic efficiency in asymmetric cells. The ND@Zn||MnO2 full cell achieves a stable life of 1000 cycles with 87.0% capacity retention at 1 A g−1 current density. This cost‐effective fabrication process holds the potential for scalability, making it amenable to large‐scale production of zinc metal anodes.

Pioneering the direct large‐scale laser printing of flexible “graphenic silicon” self‐standing thin films as ultrahigh‐performance lithium‐ion battery anodes

AbstractRecent technological advancements, such as portable electronics and electric vehicles, have created a pressing need for more efficient energy storage solutions. Lithium‐ion batteries (LIBs) have been the preferred choice for these applications, with graphite being the standard anode material due to its stability. However, graphite falls short of meeting the growing demand for higher energy density, possessing a theoretical capacity that lags behind. To address this, researchers are actively seeking alternative materials to replace graphite in commercial batteries. One promising avenue involves lithium‐alloying materials like silicon and phosphorus, which offer high theoretical capacities. Carbon–silicon composites have emerged as a viable option, showing improved capacity and performance over traditional graphite or pure silicon anodes. Yet, the existing methods for synthesizing these composites remain complex, energy‐intensive, and costly, preventing widespread adoption. A groundbreaking approach is presented here: the use of a laser writing strategy to rapidly transform common organic carbon precursors and silicon blends into efficient “graphenic silicon” composite thin films. These films exhibit exceptional structural and energy storage properties. The resulting three‐dimensional porous composite anodes showcase impressive attributes, including ultrahigh silicon content, remarkable cyclic stability (over 4500 cycles with ∼40% retention), rapid charging rates (up to 10 A g−1), substantial areal capacity (>5.1 mAh cm−2), and excellent gravimetric capacity (>2400 mAh g−1 at 0.2 A g−1). This strategy marks a significant step toward the scalable production of high‐performance LIB materials. Leveraging widely available, cost‐effective precursors, the laser‐printed “graphenic silicon” composites demonstrate unparalleled performance, potentially streamlining anode production while maintaining exceptional capabilities. This innovation not only paves the way for advanced LIBs but also sets a precedent for transforming various materials into high‐performing electrodes, promising reduced complexity and cost in battery production.

A stacking-based ensemble learning model for kneading paste quality intelligent prediction: A real case study

Paste kneading is a vital process of prebaked carbon anode production, and the quality of the paste has a great impact on the quality of the final product. However, it is difficult to inspect the paste quality in line. Because the inspection of the paste quality in the laboratory is not real-time, the paste has already entered the next process after the results are obtained. And the manual quality inspection is labor-intensive and unsafe. Therefore, a stacking-based ensemble learning model for kneading paste quality prediction is proposed in this paper. The gradient boosting decision tree, random forest, k-nearest neighbors, and support vector machine are used as base learners, and logistic regression is used as meta-learner. Kneading production data of 572 paste pots are collected for quality prediction, where each pot of paste data contains 44 signals. The correlation coefficient-based feature engineering method was applied, and 10 features with the greatest correlation with paste quality were identified to construct the dataset. The up-sampling and under-sampling methods are used to solve the problem of sample imbalance. Parallel comparison is applied to verify the advantage of the stacking-based ensemble learning model, and the results indicate that the model performs better than every single classifier and has higher accuracy and generalization ability, especially for imbalanced samples.

Coupling ultrafine TiO2 within pyridinic-N enriched porous carbon towards high-rate and long-life sodium ion capacitors

Coupling TiO2 within N-doped porous carbon (NPC) is essential for enhancing its Na+ storage performance. However, the role of different N configurations in NPC in improving the electrochemical performance of TiO2 is currently unknown.In this study, melamine is deliberately incorporated as a pore-forming agent in the self-assembly process of metal organic framework precursors (NH2-MIL-125(Ti)). This intentional inclusion of melamine leads to the one-pot and in-situ formation of highly active edge-N, which is vital for the development of TiO2/NPC with exceptional reactivity. Electrochemical performance characterization and density functional theory (DFT) calculation indicate that the interaction between TiO2 and pyridinic-N enriched NPC can effectively narrow the bandgap of TiO2/NPC, thereby significantly improving electron/ion transfer. Additionally, the abundant mesoporous channels, high N content and oxygen vacancies also contribute to the fast reaction kinetics of TiO2/NPC. As a result, the optimized TiO2/NPC-M, with high proportion of pyridinic-N (44.1 %) and abundant mesoporous channels (97.8 %), delivers high specific capacity of 282.1 mA h−1 at 0.05 A g−1, superior rate capability of 177.3 mA h−1 at 10 A g−1, and prominent capacity retention of 89.3 % over 5000 cycles even under ultrahigh 10 A g−1. Furthermore, the TiO2/NPC-M//AC sodium ion capacitors (SIC) device achieves a high energy density of 136.7 Wh kg−1 at 200 W kg−1. This research not only offers fresh perspectives on the production of high-performance TiO2-based anodes, but also paves the way for customizing other active materials for energy storage and beyond.

Anodic peroxide production for advanced oxidation processes with different metal oxide electrodes in carbonate electrolytes

Anodic electrochemical peroxide generation is promising for AOP applications. This study evaluates the electrochemical efficiency and oxidizing power of the resulting peroxide mixtures, depending on the electrolyte composition.

In-situ oxygen generation using Titanium foam/IrO2 electrode for efficient sulfide control in sewers

Hydrogen sulfide (H2S) causes corrosion of pipeline network and endangers sewer’s normal operation, while the rehabilitation or replacement of sewer network incurs expensive manpower and material costs. Conventional chemical dosing strategies such as oxygen injection and caustic soda addition, confront issues with transport and storage of chemical reagents as well as dose control. In contrast, electrochemical treatment techniques have evoked growing attention in sewer management due to its capacity of in-situ effective agent production, real-time dose control and amenability to automation. In this study, the performances of anodic oxygen production using Ti/IrO2 and Titanium foam/IrO2 as electrodes were investigated. Titanium foam/IrO2 electrode exhibited the superior oxygen evolution capacity, with the dissolved oxygen (DO) level attained in the range 8–9 mg L-1 (i.e., higher than that of 5–6 mg L-1 by Ti/IrO2 electrode). It was also indicated that a decrease in flow rate or an increase in current density would accelerate its in-situ oxygen production. DO production with the presence of COD, NH4+, HCO3−, H2PO4−/HPO42− was approximately 6.78–8.37 mg L-1. Moreover, this electrochemical method was illustrated to successfully achieve sulfide removal efficiency of 90 % in the simulated sewage experiment. The cathode compartment simultaneously produced caustic soda (∼0.4 wt% in 210 min), thereby contributing to further sulfide removal. Additionally, the effect of real sewage with different conductivities on sulfide removal proved the wide applicability of electrochemical technology in sewer management. Overall, this study demonstrated the practical potential of concurrent in-situ anodic oxygen production and cathodic caustic soda generation for sulfide control in sewers.