Cobalt Oxide Research Articles

Recycling the Spent Lithium-ion Battery into Nanocubes Cobalt Oxide Supercapacitor Electrode

Background:: Cobalt oxide nanocubes have garnered significant attention as potential supercapacitor electrodes due to their unique structural and electrochemical properties. The spent lithium-ion batteries (LiBs) are considered as zero-cost source for cobalt oxide production. Objective:: The aim of this work is to recover cobalt oxide from spent LiBs and study its electrochemical performance as a supercapacitor electrode material. Method:: This study uses an electrodeposition method to obtain cobalt oxide honeycomb-like anodes coated on Ni foam substrates from spent Li-ion batteries for supercapacitors applications. The effect of annealing temperature on the cobalt oxide anode has been carefully investigated; 450 ºC annealing temperature results in nanocubes on the surface of the cobalt oxide electrode. X-ray diffraction confirmed the formation of the Co3O4-NiO electrode. Results:: The Co3O4-NiO nanocubes electrode has shown a high specific capacitance of 1400 F g-1 at 1 A g-1 and high capacitance retention of ~96 % after 2250 cycles at a constant current density of 10 A g-1 compared to 900 F g-1 at 1 A g-1 as for prepared Co3O4 honeycomb. Conclusion:: This strategy proves that the paramount importance of Co3O4-NiO nanocubes, meticulously synthesized at elevated temperatures, as a supremely effective active material upon deposition onto transition metal foam current collectors, establishing their indispensability for supercapacitor applications.

Advancements in cobalt‐based oxide catalysts for soot oxidation: Enhancing catalytic performance through modification and morphology control

AbstractThe widespread use of diesel engines results in significant environmental contamination due to emitted pollutants, particularly soot particles. These pollutants are detrimental to public health. At present, one of the most effective ways to remove soot particles is the catalytic diesel particulate filter after‐treatment technology, which requires the catalyst to have superior low temperature activity. Compared with cerium oxide which is widely used, cobalt oxide in transition metal oxides has been widely studied in recent years because of its high redox ability and easy to control morphology. This paper elaborates on the influence of modification techniques such as doping, loading, and solid solution on the catalytic performance of cobalt‐based catalysts in soot oxidation. Along the same lines, it further reviews the research progress on cobalt‐based oxide catalysts with specific dimensional structures and morphologies in soot oxidation. Finally, it provides an outlook on the challenges faced by the theoretical basis and applied research of cobalt‐based catalysts in soot oxidation.

Operando Surface X‐Ray Diffraction Studies of Epitaxial Co3O4 and CoOOH Thin Films During Oxygen Evolution: pH Dependence

AbstractTransition metal oxides, especially cobalt oxides and hydroxides, are of great interest as precious metal free electrode materials for the oxygen evolution reaction (OER) in electrochemical and photoelectrochemical water splitting. Here, we present detailed studies of the potential‐ and pH‐dependent structure and structural stability of Co3O4 and CoOOH in neutral to alkaline electrolytes (pH 7 to 13), using operando surface X‐ray diffraction, atomic force microscopy, and electrochemical measurements. The experiments cover the pre‐OER and OER range and were performed on epitaxial Co3O4(111) and CoOOH(001) films electrodeposited on Au(111) single crystal electrodes. The CoOOH films were structurally perfectly stable under all experimental conditions, whereas Co3O4 films exhibit at all pH values reversible potential‐dependent structural transformations of a sub‐nanometer thick skin layer region at the oxide surface, as reported previously for pH 13 (F. Reikowski et al., ACS Catal. 2019, 9, 3811). The intrinsic OER activity at 1.65 V versus the reversible hydrogen electrode decreases strongly with decreasing pH, indicating a reaction order of 0.2 with respect to [OH−]. While the Co3O4 spinel is stable at pH 13, intermittent exposure to electrolytes with pH≤10 results in dissolution as well as gradual degradation of its OER activity in subsequent measurements at pH 13.

Tuning structural and optical properties of GO@Mn-doped Co3O4 hybrid nanocomposite by a facile synthesis

Metal and metal oxide materials are mostly used to tune the optical characteristics. The optical and systemic effects of pure Cobalt Oxide (Co3O4) are examined by knocking out the dissimilar assemblage of Manganese (Mn) ions using the co-precipitation method. Graphene oxide (GO) reduces the optical band gap and enhances the effects of ethical Co3O4 and MnCo3O4 by hydrothermal procedure. The percentage of Mn over pure Co3O4 was 0.09wt.%, 0.18wt.%, 0.27wt.%, and GO doped over MnCo3O4 was 1wt.%. Remarkably, spinel-type cobalt oxide has two participation band gaps at 494nm and 772nm of nanocomposites which then shifted from 494nm to 510nm and 772nm to 779nm with the doping of GO. The result describes that the band gap was minimized from 1.76eV to 1.59eV respectively to accommodate the density of states by doping of Mn ions and GO. Conductivity and optical absorbance were also increased by doping assemblage of Mn ions and GO. XRD peaks show the FCC crystalline structure of Co3O4, and the GO peak disappeared for @MnCo3O4, indicating that GO was completely reduced to rGO during the synthesis process.

3D Binder-Free Mo@CoO Electrodes Directly Manufactured in One Step via Electric Discharge Machining for In-Plane Microsupercapacitor Application

Cobalt oxide-based in-plane microsupercapacitors (IPMSCs) stand out as a favorable choice for various applications in energy sources for the Internet of Things (IoT) and other microelectronic devices due to their abundant natural resources and high theoretical specific capacitance. However, the low electronic conductivity of cobalt oxide greatly hinders its further application in energy storage devices. Herein, a new manufacturing method of electric discharging machining (EDM), which is simple, safe, efficient, and environment-friendly, has been developed for synthesizing Mo-doped and oxygen-vacancy-enriched Co-CoO (Mo@Co-CoO) integrated microelectrodes for efficiently constructing Mo@Co-CoO IPMSCs with customized structures in a single step for the first time. The Mo@Co-CoO IPMSCs with three loops (IPMSCs3) exhibited a maximum areal capacitance of 30.4 mF cm−2 at 2 mV s−1. Moreover, the Mo@Co-CoO IPMSCs3 showed good capacitive behavior at a super-high scanning rate of 100 V s−1, which is around 500–1000 times higher than most reported CoO-based electrodes. It is important to note that the IPMSCs were fabricated using a one-step EDM process without any assistance of other material processing techniques, toxic chemicals, low conductivity binders, exceptional current collectors, and conductive fillers. This novel fabrication method developed in this research opens a new avenue to simplify material synthesis, providing a novel way for realizing intelligent, digital, and green manufacturing of various metal oxide materials, microelectrodes, and microdevices.

Revitalizing E-waste: Eco-friendly electrochemical sensor for Hg(II) detection enhanced by oxygen vacancy in metal oxide nanostructures based on recycled LCD

In the current work, an innovative eco-friendly sensor using ceria integrated cobalt oxide nanosheets immobilized on LCD monitor (Ce@Co-EcoR) recycled from E-waste is presented. The Ce@Co-EcoR nanocomposite was thoroughly investigated using appropriate characterization techniques. This nanostructured electrode was employed to construct an electrochemical sensor to detect mercury. It showed a very low detection limit of 2.8 ppb, a wide detection ranges from 16 to 620 ppb, and a good sensitivity of 158.28 μA cm2.ppm−1. The sensor applicability was verified by performing interference, repeatability, stability studies. It was also applied to control the purity of sea water. This work underscores the potential of incorporating recycled materials onto sensor technology, not only to control environmental pollution, but also to promote sustainable practices in scientific innovation.

High-fidelity reconstruction of porous cathode microstructures from FIB-SEM data with deep learning

Accurate modeling of lithium-ion battery (LIB) electrode microstructures provides essential references for understanding degradation mechanisms and optimizing materials. Traditional segmentation methods often struggle to accurately capture the complex microstructures of porous LIB electrodes in focused ion beam scanning electron microscopy (FIB-SEM) data. In this work, we develop a deep learning model based on the Swin Transformer to segment FIB-SEM data of a lithium cobalt oxide electrode, utilizing fused secondary and backscattered electron images. The proposed approach outperforms other deep learning methods, enabling the acquirement of 3D microstructure with reduced particle elongated artifacts. Analyses of the segmented microstructures reveal improved electrode tortuosity and pore connectivity crucial for ion and electron transport, emphasizing the necessity of accurate 3D modeling for reliable battery performance predictions. These results suggest a path toward voxel-level degradation analysis through more sensible battery simulation on high-fidelity microstructure models directly twinned from real porous electrodes.

Synergistic effects of MXene and Co3O4 in composite electrodes: High-performance energy storage solutions

The development of high-performance electrode materials is crucial for advancing supercapacitor technology. The two-dimensional layered structure of MXene (Ti3C2Tx) presents high conductivity, abundant surface functional groups and accessible ion interaction between layers. However, the MXene suffers from the layer aggregation. To overcome this issue, we synthesized a composite material combining MXene with cobalt oxide (Co3O4) to enhance electrochemical performance in supercapacitors. MXene’s two-dimensional layered structure, high conductivity, and abundant surface functional groups allow for efficient ion intercalation, while Co3O4 contributes high theoretical capacitance and rich oxidation states. The resulted MXene/Co3O4 composite exhibits an impressive areal capacitance of 6.456F/cm2 at a current density of 3 mA/cm2, maintaining 90.52 % capacitance retention at 30 mA/cm2, and 81.37 % capacity after 5000 charge–discharge cycles. Additionally, the asymmetric supercapacitor (ASC) device fabricated using the MXene/Co3O4 composite achieves a power density of 6.41 mW/cm2 at an energy density of 0.37 mWh/cm2, with 82.3 % capacitance retention after 5000 cycles. These results demonstrate that the MXene/Co3O4 composite material is a promising candidate for high-performance supercapacitors, offering significant improvements in rate capability and long-term cycling stability.

Outstanding Activity and Durability of Supported NiCo2O4 Nanoparticles for Direct Ethanol Fuel Cells

ABSTRACTThe rational design of noble metal‐free electrocatalysts represents one of the basic stones for fuel cell development. With the exploration of eco‐friendly nanomaterials for the investigated alcohol oxidation process, nickel‐based electrodes have been recognized as the most auspicious anodes with promoted activity and stability. In this work, a series of NiCo2O4 nanoparticles were deposited onto graphite sheets (NiCo2O4/T) introducing varied proportions of cobalt oxide species. Co‐precipitation protocol of the respective metallic hydroxides onto the carbonaceous support was followed with consecutive annealing in an air atmosphere at 400°C. The fabricated mixed metallic oxide nanopowder was physically studied using X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X‐ray analysis (EDX), X‐ray photoelectron spectroscopy (XPS), and selected area electron diffraction (SAED). Uniformly arranged nanoparticles were observed on graphite surface as evidenced by SEM and TEM. The cubic lattice structure of formed NiCo2O4 crystals was also confirmed by XRD through the defined peaks of binary metallic oxides clarifying their successful preparation scheme. The electrocatalytic properties of these NiCo2O4/T nanocatalysts were evaluated for oxidizing ethanol molecules in basic solution. Pronounced oxidation current densities were remarkably measured at NiCo2O4/T electrodes in relation to that at NiO/T. Differing the introduced cobalt oxide content into the synthesized nanocatalyst significantly controlled its catalytic performance. NiCo2O4/T‐20 exhibited the highest activity and stability among the prepared nanomaterials. Much decreased charge transfer resistances were also recorded at this electrode demonstrating its promoted electron transfer characteristics. This work could provide a reasonable route for the simple synthesis of comparable transition metallic oxides with promising attitudes for energy generation purposes.

Physical and chemical characteristics and activity of nickel-modified cobalt-iron-containing catalysts in the reaction of dry reforming of methane

In the process of dry reforming of methane (DRM), the activity of low-percentage catalysts based on cobalt and iron oxides and their modification with nickel oxide was studied. It has been established that the addition of nickel oxide into the Fe2O3/γ-Al2O3 catalyst increases the degree of methane conversion from 14 to 89%, and also increases the yield of target reaction products H2 to 43.0 vol.%, CO to 46.1 vol.% at 850 °C. On a Co3О4-NiО/γ-Al2O3 catalyst at 850 °C, methane conversion reaches to 88.1%, the yield of H2 and CO is 44.8%. TPR-H2 analyzes showed that the introduction of nickel oxide into Fe2O3/γ-Al2O3 composition, in contrast to the Co3O4/γ-Al2O3 catalyst, the temperature peaks of Fe2O3-NiО/γ-Al2O3, reduction shift towards lower temperatures and weaken the interaction of metals with the support - γ-Al2O3 and thereby the amount of active reduced particles of iron and nickel oxides increases, which ensures good catalytic activity of Fe2O3-NiО/γ-Al2O3. According to the XRD results, spinel-like form - NiFe2O4, NiAl2O4 and CoAl2O4, also phase as Fe2O3 were obtained on the Fe2O3-NiО/γ-Al2O3 catalyst. This indicates that the developed catalysts form new phases that are active at high temperatures to produce synthesis gas in reduction-oxidation processes during the DRM reaction.

A Family of Twisted Chiral Engineered Inorganic Nanoarchitectures.

Chiral inorganic materials possess unique asymmetric properties that could significantly impact various fields. However, their practical application has been hindered by challenges in creating structurally robust chiral materials. We report the synthesis of well-defined chiral-shaped hollow cobalt oxide nanostructures, extendable to a family of chalcogenides including sulfide, selenide, and telluride through topological transformations. Taking chiral cobalt oxide nanostructures as a representative material, we demonstrate precise control over their chiral architectures, enabling fine-tuning of parameters, such as twist degrees, handedness, and compositions. These chiral nanostructures exhibit high spin selectivity effects that influence the electron transfer processes in catalytic reactions. Leveraging this spin-selective behavior, the chiral cobalt oxide nanoarchitectures demonstrate enhanced electrocatalytic performance in the oxygen evolution reaction compared to their achiral counterparts. Our findings not only expand the library of chiral inorganic materials but also advance the application of chiral effects in fields such as catalysis, spintronics, and beyond.

Fabrication of polyoxometalate dispersed cobalt oxide nanowires for electrochemically monitoring superoxide radicals from Hela cell mitochondria

An ultrasensitive electrochemical sensor is constructed by electrostatically adsorbing negatively charged hourglass-shape Cu-Polyoxometalate (POM) onto a positively charged CoO nanowires modified carbon cloth. The petaloid CoO nanowires have a large specific surface area that can well disperse open-structured Cu-POM to form Cu-POM@CoONWs@CC, which can maximumly expose catalytic active centers (Co2+ and Cu2+) and accelerate mass/charge transfer. In addition to the above advantages, the excellent electron exchange ability of Cu-POM and good conductivity of CoONWs@CC endow the sensor with good detection capability to H2O2 including a linear detection range of 0.05–1.4 μA μM−1, a low detection limit of 0.022 μM, high sensitivity of 110.48 μA μM−1, good selectivity and long-term stability. Due to the fast transformation of superoxide anion (O2∙‐) to H2O2, the sensor can indirectly monitor the electron leakage resulting in the formation of O2∙‐ via detecting H2O2. Afterwards, Hela cell mitochondria were extracted from the living cells that cultured with different mitochondrial inhibitors and the release of O2∙‐ from the corresponding mitochondrial complexes was monitored by the sensor. Through comparing the current signals, we determined that complex I is probably the main electron leakage site. This work could provide meaningful information for the diagnosis of certain oxidative stress diseases.

A Universal Plug-and-Play Approach to In Situ Multinuclear Magnetic Resonance Analysis of Electrochemical Phenomena in Commercial Battery Cells.

Advancing electrochemical energy storage devices relies on versatile analytical tools capable of revealing the molecular mechanisms behind the function and degradation of battery materials in situ. The nuclear magnetic resonance phenomenon plays a pivotal role in fundamental studies of energy materials and devices because of its exceptional sensitivity to local environments and the dynamics of many electrochemically relevant elements. The jelly roll architecture is one of the most energy-dense and, therefore, most popular concepts implemented in pouch, prismatic, and cylindrical Li- and Na-ion cells. Such widely commercialized designs, however, represent a significant obstacle for a range of powerful in situ magnetic resonance-based methodologies due to negligible radio frequency electromagnetic field penetration through conductive metal casings and current collectors. In this work, we introduce an experimental setup that enables direct RF wave transmission through the cell terminals and current collectors, and provides efficient excitation and detection of NMR signals. An RF adapter designed as a plug-and-play device effectively turns the battery cell into an NMR probe that can be tuned to a broad range of Larmor frequencies. Due to its exceptional sensitivity, versatility, and multinuclear capability, the proposed methodology is suitable for fundamental research and industrial high-throughput screening applications. In situ NMR lineshapes provide a direct quantitative description of the chemical environments of electrochemically active elements and enable new metrics for the accurate assessment of state-of-charge (SoC) and state-of-health (SoH). Specifically, in commercial pouch cells based on lithium cobalt oxide, lithium nickel manganese cobalt oxide, and sodium nickel iron manganese oxide chemistries, 7Li and 23Na NMR data unambiguously show electrochemical transformations between intercalated and metallic forms of charge carrier ions, and reveal anisotropic magnetic properties of the electrode coating.

Regulating solvated sheath with anion chelant enables 4.6 V ultra-stable commercial LiCoO2.

Increasing cut-off voltage of lithium cobalt oxide (LCO) (> 4.6 V) is an effective strategy to satisfy the ever-increasing demand for high energy density. However, the irreversible phase transition significantly destroys the structure of high-voltage LCO, especially the surface lattice. Considering that the structural stability of LCO is primarily dominated by the intrinsic merits of electrode-electrolyte interface (EEI), we explored and disclosed the operating mechanism of anion chelating agent tris(pentafluorophenyl) borane (TPFPB) and regulate the CEI layer on LCO electrode. Benefiting from the high HOMO energy level and preferential decomposition of TPFPB-PF6-, a robust LiF-rich CEI layer is constructed and greatly improves the stability of electrode/electrolyte interface. The well-designed electrolyte composed of 1 mol L-1 LiPF6 in EC/EMC with TPFPB additives endows Li/LCO half cells and 4 Ah Gr/LCO pouch cell with enhanced cycling stability under a high voltage condition. This work provides pave a new direction for the development of economical high-voltage LIBs.

Electrochemical evaluation of cobalt oxide incorporated MoS2 ex/PANI ternary composite as a promising electrode for high-performance symmetric and asymmetric supercapacitors

Electrochemical evaluation of cobalt oxide incorporated MoS2 ex/PANI ternary composite as a promising electrode for high-performance symmetric and asymmetric supercapacitors

Characterization of Lithium-Ion Battery Fire Emissions—Part 2: Particle Size Distributions and Emission Factors

The lithium-ion battery (LIB) thermal runaway (TR) emits a wide size range of particles with diverse chemical compositions. When inhaled, these particles can cause serious adverse health effects. This study measured the size distributions of particles with diameters less than 10 µm released throughout the TR-driven combustion of cylindrical lithium iron phosphate (LFP) and pouch-style lithium cobalt oxide (LCO) LIB cells. The chemical composition of fine particles (PM2.5) and some acidic gases were also characterized from filter samples. The emission factors of particle number and mass as well as chemical components were calculated. Particle number concentrations were dominated by those smaller than 500 nm with geometric number mean diameters below 130 nm. Mass concentrations were also dominated by smaller particles, with PM1 particles making up 81–95% of the measured PM10 mass. A significant amount of organic and elemental carbon, phosphate, and fluoride was released as PM2.5 constituents. The emission factor of gaseous hydrogen fluoride was 10–81 mg/Wh, posing the most immediate danger to human health. The tested LFP cells had higher emission factors of particles and HF than the LCO cells.

Efficiency of Penicillium sp. and Aspergillus sp. for bioleaching lithium cobalt oxide from battery wastes in potato dextrose broth and sucrose medium

Lithium-ion batteries, a primary power source, generate electronic hazardous waste at the end of their lifespan, which is a richer source of highly concentrated metals such as cobalt and lithium than those in natural resources. The waste is a potential renewable resource for the extraction of metals. Bioleaching, a process utilizing microbial activity, was used in this study to investigate the cobalt and lithium leaching efficiency from battery wastes. Two fungal strains, Aspergillus sp. strain JMET 15 and Penicillium sp. strain JMET 24 were used with different organic carbon sources (sucrose medium and potato dextrose broth) at 1 % pulp density. The sucrose medium derived a higher acid quantity and leached higher concentration of cobalt and lithium than in potato dextrose broth. Leaching efficiency by JMET 24 was higher than JMET 15. Cobalt (32.57 % and 27.19 %) and lithium (65.07 % and 40.58 %) were bioleached by JMET 24 and JMET 15, respectively, after 30 d cultivation in the sucrose medium. Lower pulp density was conducted to achieved higher leaching efficiency by JMET24, cobalt (77.87 % and 74.5 %) and lithium (99.88 % and 78.4 %) were bioleached at 0.1 % and 0.5 % pulp density, respectively. Cobalt oxide (Co3O4) was the product of the one-step recovery (leaching and precipitation) process. Cobalt was transformed from lithium cobalt oxide to cobalt phosphate-oxalate by JMET 24 in the sucrose medium. Thus, the potential of bioleaching as an effective method for recovering valuable metals from lithium-ion battery waste is demonstrated, presenting a promising approach for both waste management and resource recovery.

Unraveling the Electrochemical Insights of Cobalt Oxide/Conducting Polymer Hybrid Materials for Supercapacitor, Battery, and Supercapattery Applications.

This review article focuses on the potential of cobalt oxide composites with conducting polymers, particularly polypyrrole (PPy) and polyaniline (PANI), as advanced electrode materials for supercapacitors, batteries, and supercapatteries. Cobalt oxide, known for its high theoretical capacitance, is limited by poor conductivity and structural degradation during cycling. However, the integration of PPy and PANI has been proven to enhance the electrochemical performance through improved conductivity, increased pseudocapacitive effects, and enhanced structural integrity. This synergistic combination facilitates efficient charge transport and ion diffusion, resulting in improved cycling stability and energy storage capacity. Despite significant progress in synthesis techniques and composite design, challenges such as maintaining structural stability during prolonged cycling and scalability for mass production remain. This review highlights the synthesis methods, latest advancements, and electrochemical performance in cobalt oxide/PPy and cobalt oxide/PANI composites, emphasizing their potential to contribute to the development of next-generation energy storage devices. Further exploration into their application, especially in battery systems, is necessary to fully harness their capabilities and meet the increasing demands of energy storage technologies.

Synergistic Effect of Cobalt/Ferrocene as a Catalyst for the Oxygen Evolution Reaction.

There is a great deal of interest in the development of electrocatalysts for the oxygen evolution reaction (OER) that are stable and have high activity because this anodic half-reaction is the main bottleneck in water splitting and other key technologies. Cobalt and iron oxide and oxyhydroxide electrocatalysts constitute a cheaper alternative to the highly active and commonly used Ir- and Ru-based catalysts. Most of the described electrocatalysts require tedious synthetic and expensive preparation procedures. We report here a facile and straightforward preparation of an electrocatalyst by a combination of commercial compounds, such as cobalt chloride and ferrocene. A highly active and stable OER electrocatalyst is obtained, which shows a low overpotential in the alkaline medium as a consequence of a synergistic effect between both compounds and is inexpensive.

Metal-decorated opal-like silica catalysts: High-temperature reconstructions in cobalt-ceria active layer during simultaneous oxidation of CO and hydrocarbons

Opal-like silica, which represents a new class of SiO2-based nanomaterials, was used as a support for the deposition of cobalt and cerium oxides as active components. A series of samples was prepared and tested in the oxidation of CO and hydrocarbons in a prompt thermal aging regime. As revealed by a set of physicochemical methods, the initial catalytic performance of the samples is high (T50 = 214 °С) due to the emergence of new catalytic sites, which appeared as a result of interaction between Co and Ce oxides located between silica nanospheres in a close proximity to each other. At 800 °C, these particles undergo agglomeration, which is expressed in a slight deactivation of the catalysts (T50 ≥ 260 °С). The bulk silicate phase is formed at 900 °C, thus leading to further deactivation. Recovering of the catalytic activity (T50 = 252 °С) takes place at 1000 °С.