Simple Ball Milling Research Articles

Oxygen Vacancies of Commercial V2O5 Induced by Mechanical Force to Enhance the Diffusion of Zinc Ions in Aqueous Zinc Battery

AbstractRechargeable aqueous batteries with Zn2+ as a media‐ion are promising candidates for large‐scale energy storage because of their intrinsic safety, low‐cost and high energy‐intensity. Vanadium based cathodic materials have gained significant attention in aqueous zinc‐ion batteries (AZIBs) due to their high capacity and satisfactory cycle stability. However, more facile and efficient fabrication methods should be explored when considering future realistic application. Herein, commercial V2O5 cathodes with oxygen vacancies were fabricated through a simple mechanical ball milling method. The results suggest that mechanical force can directly induce the oxygen vacancies in commercial V2O5, which significantly enhance the diffusion of Zn ions. The oxygen vacancy−V2O5 (Ov−V2O5) shows much higher capacity than the pristine commercial V2O5 and the cyclic stability reached 2500 times. Ov−V2O5 cathode with a facile synthesis technology is a promising candidate for future high‐performance, low‐cost, safe, and environment‐friendly Zn battery devices.

Fe2O3 supported Pt single atom catalysts for the selective hydrogenation of cinnamaldehyde.

Atomically dispersed Pt species supported on Fe2O3 (Pt1/Fe2O3) are successfully constructed by a simple ball milling process. In the selective hydrogenation of cinnamaldehyde (CAL), Pt1/Fe2O3 achieves an excellent cinnamyl alcohol (COL) selectivity of 81.7% at a CAL conversion of 91.2% in pure water medium due to the superior dissociation ability of H2 and preferential adsorption of CAL via CO.

Structural and Electrochemical Properties of Physically and Chemically Activated Carbon Nanoparticles for Supercapacitors.

The demand for supercapacitors has been high during the integration of renewable energy devices into the electrical grid. Although activated carbon materials have been widely utilized as supercapacitor electrodes, the need for economic and sustainable processes to extract and activate carbon nanomaterials is still crucial. In this work, the biomass waste of date palm fronds is converted to a hierarchical porous nanostructure of activated carbon using simple ball-milling and sonication methods. Chemical and physical activation agents of NaOH and CO2, receptively, were applied on two samples separately. Compared with the specific surface area of 603.5 m2/g for the CO2-activated carbon, the NaOH-activated carbon shows a higher specific surface area of 1011 m2/g with a finer nanostructure. Their structural and electrochemical properties are functionalized to enhance electrode–electrolyte contact, ion diffusion, charge accumulation, and redox reactions. Consequently, when used as electrodes in an H2SO4 electrolyte for supercapacitors, the NaOH-activated carbon exhibits an almost two-fold higher specific capacitance (125.9 vs. 56.8 F/g) than that of the CO2-activated carbon at the same current density of 1 A/g. Moreover, using carbon cloth as a current collector provides mechanical flexibility to our electrodes. Our practical approach produces cost-effective, eco-friendly, and flexible activated carbon electrodes with a hierarchical porous nanostructure for supercapacitor applications.

Synthesis and characterization of chlorinated hydroxyapatite as novel synthetic bone substitute with negative zeta potential

In the present work, chlorine doped hydroxyapatite (ClHA), with varying degrees of ion replacement was successfully synthesized by a simple ball milling technique. The resulting powders were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Field emission scanning electron microscopy and particle size analyzer. The zeta potential of the powders was performed in physiological saline (0.154 M). The results confirmed the formation of apatite as the main phase in all chlorine substituted powders except for some incremental changes in the lattice parameter ‘a’ and unit cell volumes of the resultant powders. However, the crystallinity of the powders declined from 96% to 83%. Fourier transform infrared spectroscopy results confirmed the incorporation of Cl ions in the apatite lattice by the appearance of new bands at 677 cm-1. FESEM results revealed that the crystallites have grown into grains with no major agglomeration. Vicker hardness test results revealed a hardness value of 2.65 ± 0.258 GPa for ClHA4 dense bodies at a load of 200g. Zeta potential analysis of the powders suggested that ClHA nanopowders can prove to be a potential bone implant material.

Synergistic Combination of TiO2 and S-PAN for Li-S Batteries with Long-Term Cyclability at High C-Rates

A ternary compound was synthesized from titanium dioxide, elemental sulfur and polyacrylonitrile throughout a simple ball-milling and heating process in inert atmosphere, and was fully characterized. The novel compound belongs to the family of sulfurized polyacrylonitrile compounds (SPAN) and was incorporated as active material in the cathode of Li-S batteries. The cells achieve high and stable capacity values at 0.5 C reaching 1885 mAh gS −1 for the 10th cycle and ∼1600 mAh gS −1 after 200 cycles (498 and 422 mAh g−1 composite, respectively). To the best of our knowledge, we are the first ones to report the combination of SPAN and TiO2, and to show the synergistic behaviour of these compounds. The high capacity values observed, higher than the theoretical capacity of elemental sulfur (1675 mAh g−1), are explained by the extra capacity provided by the lithiation/delithiation process of TiO2. The metallic oxide also improves the overall kinetics of the redox processes in SPAN, which helped to achieve good cycling performance at 3.3 C, with a remaining capacity of 672 mAh gS −1 after 1400 cycles, and even at 5 C where a remaining capacity of 660 mAh gS −1 after 500 cycles was recorded.

Influence of the LiFePO4/C coating on the electrochemical performance of Nickel-rich cathode for lithium-ion batteries

LiFePO4/C (LFP/C)-coated LiNi0.8Co0.1Mn0.1(NCM811) was prepared by a simple ball milling method (400 rpm for 4 h), and the influence of different coating amounts of LFP/C on the electrochemical performance of NCM811 was studied in detail. When the LFP/C coating amount was 1 wt%, the material maintained good electrochemical cycling stability and rate performance. The capacity retention of NCM811 @ 1LFP/C after 300 cycles was 61.6% at 25 ℃, which was significantly better than the corresponding value of 48.63% of NCM811. Simultaneously, the high temperature (55 ℃) and high pressure (2.8–4.5 V) cycling stability performance of NCM811 @ 1LFP/C was also better than for uncoated materials. The EIS results showed that the 1LFP/C modification effectively reduced RSEI (from 46.37 to 32.13 Ω) and Rct (from 155.9 to 113.5 Ω), which was beneficial for the interface charge transfer of electrons and Li+ ions, consistent with the CV analysis. The XRD, XPS, and FESEM results indicated that the coating layer suppressed the changes in the NCM811 particle macro-volume and reduced the side reactions, improving the electrochemical performance of Nickel-rich layered materials.

Production of multifunctional bamboo-based phase change encapsulating material by straightforward dry ball milling

Phase change materials (PCMs) have attracted much attention due to their high energy storage density and thermal efficiency. In this paper, bio-based bamboo flour (BF) and polyethylene glycol (PEG) were compounded together as a shape stable phase change material (SSPCM). A novel bamboo-based matrix for packaging organic PCMs was prepared by a simple dry ball milling process. Using the reinforcement of bamboo fiber and the porous characteristics of parenchyma cells, PEG / BF not only has high encapsulation rate, but also has high thermal conductivity. The leakage test results showed that the BF adsorption capacity with longer milling time was improved. The packaging ability of BF on PEG tended to be unchanged after 12 h of milling. The maximum loading of both PEG 4000 and 2000 in SSPCMs was 50 wt%, while PEG 10,000 was 70 wt%. The composites had good shape stability and no leakage defects. FTIR results showed that there was no new diffraction peak in composites appeared indicating that limited chemical reaction happened between BF and PEG. The results of XRD showed that the crystallinity of PEG decreased with the employ of BF. The phase transition temperature of SSPCMs measured by DSC did not depend on the content of BF. The highest melting latent heat of SSPCM was 113 J/g by PEG 10,000/30% BF and the enthalpy efficiency reached 61.08%. Continuous network structure of bamboo fiber in composites improved the thermal conductivity of the PEG/BF. The highest thermal conductivity of PEG 10,000/BF products can reach 0.64 W/m•K. The results of thermal cycle tests and TG also showed that PEG/BF had good thermal and chemical stability. The study proved that the composite had potential application value in solar energy storage combined with other materials such as polymer bamboo composites, bamboo based composites and other bamboo fiber reinforced materials.

Biodegradable L-lysine-modified amino black phosphorus/poly(l-lactide-coε-caprolactone) nanofibers with enhancements in hydrophilicity, shape recovery and osteodifferentiation properties

Biodegradable poly-(lactide-coε-caprolactone) (PLCL) scaffolds have opened new perspectives for tissue engineering due to their nontoxic and fascinating functionality. Herein, a black phosphorus-based biodegradable material with a combination of promising enhanced hydrophilicity, shape recovery and osteodifferentiation properties was proposed. First, amino black phosphorous (BP-NH2) was prepared by a simple ball milling method. Then, L-lysine-modified black phosphorous (L-NH-BP) was formed by hydrogen bonding between L-lysine and amino BP and integrated into PLCL to form PLCL/L-NH-BP composite fibers. The scaffolds had excellent shape recovery and shape fixity properties. Moreover, based on gene expression and protein level assessment, the scaffolds could enhance the expression of alkaline phosphatase (ALP) and bone morphogenetic protein 2 (BMP2), simultaneously improving the mineralization ability of bone mesenchymal stem cells. Specifically, this new composite material was experimentally verified to be degradable under mild conditions. This strategy provided new insight into the design of multifunctional materials for diverse applications.

Fabrication of Ultra-Fine-Grained W-TiC Alloys by a Simple Ball-Milling and Hydrogen Reduction Method

In this paper, a simple method to fulfill the ideal microstructural design of particle reinforced tungsten (W) alloys with promising mechanical properties is presented. W-0.5 wt.% TiC powders with core-shell (TiC/W) structure are prepared by ball-milling and controlled hydrogen reduction processes. TEM observation demonstrates that the nano TiC particles are well coated by tungsten. The W-TiC powders are sintered by spark plasma sintering (SPS) under 1600 °C. The sintered microstructures are characterized by FESEM and TEM. It is found that the W-0.5TiC alloys obtain an ultra-fine-sized tungsten grain of approximately 0.7 μm. The TiC particles with the original nano sizes are uniformly distributed both in tungsten grain interiors and at tungsten grain boundaries with a high number density. No large agglomerates of TiC particles are detected in the microstructure. The average diameter of the TiC particles in the tungsten matrix is approximately 47.1 nm. The mechanical tests of W-0.5 TiC alloy show a significantly high microhardness and bending fracture strength of 785 Hv0.2 and 1132.7 MPa, respectively, which are higher than the values obtained in previous works. These results indicate that the methods used in our work are very promising to fabricate particle-dispersion-strengthened tungsten-based alloys with high performances.

Markedly improved hydrophobicity of cellulose film via a simple one-step aminosilane-assisted ball milling

Most cellulose products lack water resistance due to the existence of abundant hydroxyl groups. In this work, microfibrillated cellulose (MFC) was modified via 3-aminopropyltriethoxysilane (APTES)-assisted ball milling. Under the synergism between high-energy mechanical force field and APTES-modification, the fibrillation and hydrophobization of MFC were achieved simultaneously. Free-standing translucent cellulose films made of modified MFC were fabricated. The original crystal form of cellulose is maintained. The hydrophobicity of cellulose film markedly increases and the water contact angle goes up to 133.2 ± 3.4°, which might be ascribed to the combined effects of APTES-modification and rough film surface. In addition, the thermostability and mechanical properties of cellulose film are also improved via mechanochemical modification. This work provides a novel one-step fibrillation-hydrophobization method for cellulose.

Reduced porous carbon/N-doped graphene nanocomposites for accelerated conversion and effective immobilization of lithium polysulfides in lithium-sulfur batteries

Lithium sulfur (Li-S) batteries have been foreseen as the next generation energy storage device because of their high theoretical energy density. However, a low-cost, efficient and replicable way for mass producing suitable host materials that enable high-performance Li-S batteries is still a huge challenge. To tackle this issue, a rPC-NG composite was fabricated by mixing reduced porous carbon material (rPC) prepared from PAN fiber and N-doped graphene (NG) through a simple and scalable ball milling process. Herein, the rPC and NG immobilize sulfur via strong physical and chemical adsorption and inhibit the shuttle effect of lithium polysulfides (LiPSs) successfully. Importantly, such composite possesses a layered porous structure which can contribute to a high loading of sulfur, leading to the excellent conductivity, outstanding utilization rate and stability of adsorbed sulfur. The resultant rPC-NG/S cathode exhibits a stable cycling performance (503 mAh g−1 at 0.5 C after 500 cycles and 770 mAh g−1 at 0.2 C after 200 cycles) and high rate performance (540 mAh g−1 at 2 C).

Unraveling improved electrochemical kinetics of In2Te3-based anodes embedded in hybrid matrix for Li-ion batteries

Although the introduction of hybrid matrices (e.g., metal oxide–carbon (e.g., TiO2–C) and metal carbide–carbon (e.g., TiC–C)) has shown to be effective for enhancing the electrochemical performance of alloy-based active materials, reliable evidence that verifies these favorable effects remain ambiguous. Herein, we propose a simple and effective strategy that can effectively resolve these issues and significantly extend the battery lifespan. To elucidate this phenomenon more clearly, In2Te3-based active materials with/without a TiO2–C matrix were prepared via simple two-step high-energy ball milling. To precisely elucidate the dynamics of Li-ion diffusion, various electrochemical techniques, including electrochemical impedance spectroscopy, cyclic voltammetry, and the galvanostatic intermittent titration technique, were used. The results indicate the synergetic roles of TiO2 and C; whereas the TiO2 phase improves the Li-ion diffusion dynamics, amorphous carbon reduces the internal resistance and volume change of the active In2Te3 material. Consequently, the In2Te3 embedded in the TiO2–C matrix (In2Te3–TiO2–C) exhibits good electrochemical performance for Li-ion storage, i.e., high specific capacity (∼846 mAh g−1 at 100 mA g−1 after 200 cycles and ∼704 mAh g−1 at 200 mA g−1 after 300 cycles), high rate capability (∼450 mAh g−1 at 10A g−1 and ∼99% capacity recovery after a series of different current densities), and good long-term cycling performance (∼435 mAh g−1 of specific capacity after 500 cycles at a high current density of 500 mA g−1), compared with three control counterpart electrodes. Therefore, the In2Te3–TiO2–C composite developed in this study is a promising anode material for next-generation LIBs.

High-Capacity CuSi2P3-Based Semisolid Anolyte for Redox Flow Batteries.

Redox flow batteries (RFBs) have attracted more attention due to their ability of decoupling energy and power, but their low energy density has greatly restricted their applications. Semisolid flow batteries (SSFBs) are a kind of RFBs, but they have high energy density. However, there is a lack of research on semisolid anolytes, and thus the application of SSFBs is still in its infancy. In this work, a low-potential (0.6 V vs Li/Li+) CuSi2P3@C-LiPAA composite is synthesized through a simple high-energy mechanical ball milling and impregnation method based on the CuSi2P3 (CSP) compound; then, it is used to prepare a semisolid anolyte, which is able to achieve a high volumetric capacity of 400 Ah L-1 in static mode and 320 Ah L-1 in intermittent-flow mode. This is the highest volumetric capacity of anolyte so far. The effect of adding binder to a composite is also discussed for the first time, which makes the connection between the composite particles closer and the semisolid suspension more uniform so as to obtain stable electrochemical performance. At the same time, through pairing respectively with two types of catholytes, liquid 10-methylphenothiazine (MPT) and semisolid LiFePO4 (LFP), a single-cell voltage of 3 V and more than 100 stable cycles with the Coulombic efficiency of 99% have been achieved by CSP-MPT and CSP-LFP full-cell systems. The result fully demonstrates the applicability of the prepared CSP semisolid anolyte. The synthesis method of adding a binder to the composite in this work also provides a direction for optimizing the suspension for other active materials to be applied to SSFBs in the future.

A novel research on the positive effects of oxygen vacancies for interstitial N-doped MnO2 on lithium-ion diffusion

In defect engineering, doping and vacancy are effective ways to improve the electrochemical performance of electrode material. For the first time, we introduce N dopants and tunable oxygen vacancies into electrolytic MnO2 with graphite as skeleton by a simple wet ball milling. The nanocomposites (NEG) exhibit excellent rate performance under various current densities. The density functional theory (DFT) calculations and climbing image-nudged elastic band (CI-NEB) demonstrate the interstitial N dopants can improve electronic conductivity and lithium-ion diffusion. This research will facilitate the deep understanding of the mechanism of lithium-ion diffusion and provide a novel idea for the study on the defect engineering.

Novel green printing of cotton, wool and polyester fabrics with natural safflower dye nanoparticles

Hiren safflower dye nanoparticles were successfully prepared by using simple ball milling technique at room temperature. UV-vis. absorption, XRD, TEM, FT-IR spectroscopy and SEM were used to characterize safflower dye nanoparticles. The prepared safflower dye nanoparticles were used as active ingredient for printing cotton, wool and polyester fabrics via dye printing technique and pigment printing technique. Factors of printing process were studied such as Mordanting of Substrates, thickeners type, urea concentration and Printing Paste pH for first paste and urea concentration, Printing Paste pH and binder concentration for second paste. Results shows fabrics printed with safflower dye nanoparticles via mentioned two methods shows very good to excellent fastness properties with full green method. These data indicated that printed samples have high quality for colour strength without any environmental hazards compared with other conventual and nanotechnological aspects.

Waste-glass-derived silicon/CNTs composite with strong Si-C covalent bonding for advanced anode materials in lithium-ion batteries

Silicon is regarded to be promising anode materials in next-generation rechargeable lithium-ion batteries due to the high theoretical capacity and natural abundance. In order to overcome intrinsic drawbacks such as the low conductivity and unstable solid electrolyte interface film, different Si and carbon (C) nanocomposites have been designed but they are often plagued by the complex structural design, high preparation cost, and weak interactions between C and Si resulting in limited electrochemical performance. Herein, a facile, eco-friendly, low-cost, and controllable route is described to prepare Si/carbon nanotube composites with strong Si-C covalent bonding from recycled waste glass and commercial carbon nanotubes (g-Si/CNTs) via simple mechanical ball milling and magnesiothermic reduction (MR). Owing to the conductive CNTs network, strong Si-C covalent bonds are formed in situ between the CNTs and Si nanoparticles and consequently, the g-Si/CNTs electrode shows an excellent specific capacity of ~895 mAh g−1 as well as 84.3% capacity retention at 0.1 A g−1 after 200 cycles. The g-Si/CNTs composite produced from recycled waste glass has large potential as anode materials in high-energy lithium-ion batteries.

Fabrication of novel Ag4Bi2O5-x towards excellent photocatalytic oxidation of gaseous toluene under visible light irradiation

In this work, a novel oxide combined with bismuth (Bi) and silver (Ag) was prepared via simple ball milling. This substance was optimized by adjusting the amount of pre-source. Preliminary characterization results confirmed the successful synthesis of Ag4Bi2O5. Subsequently, gaseous toluene was selected as model compound to evaluate the photocatalytic activity of Ag4Bi2O5 photocatalyst. According to the degradation results, Ag4Bi2O5 performed excellent visible light-driven photocatalytic activity with high stability. For the oxidation process of gaseous compound, reactive oxygen species (ROS) were responsible for the achievement, and the formation of oxygen vacancies on Ag4Bi2O5 were involved in the generation of ROS to promote the transfer of photogenerated electrons, and improving photocatalytic activity. DFT calculations revealed the theoretical band gap of Ag4Bi2O5 bulk is 1.758 eV. And the work function of Ag4Bi2O5 (112)ov was ca. at 4.447 eV. The material was easily fabricated and a reliable path was provided for the synthesis of new and efficient photocatalyst for the remediation of polluted indoor air.

A Simple Ball Milling and Thermal Oxidation Method for Synthesis of ZnO Nanowires Decorated with Cubic ZnO2 Nanoparticles.

In this work, we propose the synthesis of ZnO nanostructures through the thermal oxidation of ball-milled powders with the introduction of Mg and Sn doping species at the preliminary step of milling. We investigate the advantages and challenges of this two steps process for the production and fabrication of highly crystalline ZnO nanowires. This simple method allows us to fabricate ZnO nanowires with a higher quality core crystal at a much lower temperature and for a shorter processing time than the state-of-the-art, and decorated with by ZnO2 nanoparticles as determined via TEM analysis. The main findings will show that the crystalline core of the nanowires is of hexagonal ZnO while the nanoparticles on the surface are ZnO2 cubic type. Generally, the method proves to be suitable for applications that require a high surface-to-volume ratio, for example, catalysis phenomena, in which the presence of zinc oxides species can play an important role.

Mechanically combined persulfate on zerovalent iron: Mechanistic insights into reduction and oxidation processes

Persulfate (S2O82−; PS) has been used with zerovalent iron (ZVI) for the remediation of various contaminants. However, the passive layer of commercial ZVI limitates the corrosion of ZVI and reaction with PS. In our initial attempt, we mechanically combined Na2S2O8 and micro-sized ZVI by simple ball milling to improve the reaction of PS and ZVI. The synthesized composite (PSZVIbm) was compared to the system in which Na2S2O8 was separately injected with ball-milled ZVI (ZVIbm/PS). The reaction in ZVIbm/PS depended on surface-bound Fe(II) to initiate PS consumption. Conversely, the PS immediately destroyed the passive layer and enhanced the corrosion of ZVI in PSZVIbm. Therefore, PSZVIbm reduced nitrobenzene rapidly with higher efficiency in deionized water (94.2%) compared to that of ZVIbm/PS (73.1%). Furthermore, PSZVIbm was less affected by the real groundwater matrix and removed nitrobenzene with higher efficiency (64.7%) than ZVIbm/PS (10.3%). Due to the different PS consumption rates and radical species, PSZVIbm removed phenol with lower efficiency (22.7%) than ZVIbm/PS (61.5%), showing the different effects of surface-bound Na2S2O8 on the reduction/oxidation capacities of ZVI. This study suggests a new scalable method to control the reactivity of ZVI without the use of toxic chemicals and wastewater generation.

Enhanced catalytic microwave pyrolysis of low-rank coal using Fe2O3@bluecoke absorber prepared by a simple mechanical ball milling

Fe2O3 and bluecoke (BC) powder are used in preparing novel and cheap carbon-based absorbers through simple mechanical ball milling and by enhancing catalytic microwave pyrolysis. The electromagnetic and catalytic properties of the active compositions and matrices are controlled, and the characteristics of the prepared Fe2O3@BC absorbers and pyrolysis products are detected and analyzed in detail through SEM–EDS, XRD, FT-IR, TG-DTG, and GC-MS. Results show that most of the Fe2O3 particles aggregate and uniformly form numerous flower clusters on the surfaces of the BC fragments, developing many edges and interface structures. The presence of iron oxides and iron in BC with Fe2O3 indicates that the catalysis of Fe2O3 on coal is caused by the iron mixture. Enhancement in microwave pyrolysis significantly and rapidly increases temperature and product distribution, and the maximum tar yield of 7.94 wt% is obtained with the Fe2O3@BC absorber. Product analysis shows that the “hot spot” effect of BC and Fe2O3 and the activation of Fe2O3 on free hydrogen result in the complete microwave pyrolysis of low-rank coal and thereby improve the yield and quality of tar and coal gas. Possibly caused by the introduction of magnetic loss and “rim–edge” effect, which enhances catalytic microwave pyrolysis, the synergistic effects of Fe2O3 and BC are confirmed by theoretical calculation and experiment results. The microwave pyrolysis technology of low-rank coal is feasible because of good economic and energy efficient microwave pyrolysis of low-rank coal, and fully utilized pyrolysis products and by-products.