Jun Ming

Facile synthesis of a Co3O4-carbon nanotube composite and its superior performance as an anode material for Li-ion batteries

In this work, we report a facile method for the synthesis of a Co3O4–functionalized carbon nanotube (Co3O4–f-CNT) composite via the growth of Co3O4 nanoparticles on the surface of functionalized carbon nanotubes (f-CNTs) by thermal decomposition of cobalt nitrate hexahydrate in ethanol. The composite consists of 13% carbon nanotubes and 87% Co3O4 nanoparticles by weight, and all the Co3O4 particles grew compactly along the carbon nanotube axis with a highly uniform dispersion. When used as an anode material for rechargeable lithium ion batteries, the composite manifested high capacities and excellent cycling performance at high and low current rates. The discharge capacity was 719 mA h g−1 at the 2nd cycle and 776 mA h g−1 at the 100th cycle. Even at a current density of 1 A g−1, the specific capacity still remained at about 600 mA h g−1. This superior electrochemical performance was attributed to the unique nanostructure of the composite. Because almost all of the Co3O4 nanoparticles were immobilized on the surface of f-CNTs, physical aggregation of nanoparticles was avoided during the charge–discharge processes. Furthermore, the good mechanical flexibility of f-CNTs can readily alleviate the massive volume expansion/shrinkage associated with a conversion reaction electrode. Finally, f-CNTs are highly conductive matrices for electrons due to their high conductivity, which can shorten the diffusion path for electrons.

Selective conversion of concentrated microcrystalline cellulose to isosorbide over Ru/C catalyst

Highly concentrated microcrystalline cellulose was directly converted to isosorbide with yields of 35–50%, providing a new approach for producing important fine chemicals from biomass.

Fine control of titania deposition to prepare C@TiO2 composites and TiO2 hollow particles for photocatalysis and lithium-ion battery applications

In this study, an effective method of slow hydrolization of metal alkoxide (e.g., Ti(C4H9O)4) in an ethanol–water system was systematically investigated and used to finely control the deposition of titania on carbon colloids. A model of adsorption–hydrolization of precursors during the coating process was rationally built for the first time to interpret the usability of the method and facilitate its further extension. Using this strategy, titania in the form of supported nanocrystals or layers on carbon colloids (TiO2/C, C@TiO2) was successfully tailored. Meanwhile, finely dispersed hollow TiO2 nanoparticles with shells consisting of different crystalline structures were also prepared by varying the calcination conditions after removing the carbon cores. More importantly, the effects of the crystalline and nano/macrostructures of the as-prepared TiO2 samples in photocatalysis and lithium-ion battery applications were analyzed in detail. The preliminary results show that anatase–rutile TiO2 hollow particles demonstrate a higher catalytic activity in the photo-degradation of rhodamine B than anatase TiO2 hollow particles, powders, and P25. However, in the case of Li-ion battery applications, the anatase TiO2 hollow particles exhibited better performance as anode materials with high capacities of around 190 mA h g−1, 140 mA h g−1, and 120 mA h g−1 at current densities of 60 mA g−1, 120 mA g−1, and 300 mA g−1, respectively, accompanied by stable cyclability.

CO2–expanded ethanol chemical synthesis of a Fe3O4@graphene composite and its good electrochemical properties as anode material for Li-ion batteries

In this work, we have developed a new method to synthesize a Fe3O4@graphene (Fe3O4@GN) composite. First, the precursor was synthesized through the decomposition of ferric nitrate in the presence of graphene oxide in the mixed solvent of CO2–expanded ethanol. Then, the precursor was converted to the Fe3O4@GN composite via thermal treatment in N2 atmosphere. With the help of the CO2–expanded ethanol, Fe3O4 nanoparticles were coated on the surface of GN completely and uniformly with high loading. However, it is difficult to load Fe3O4 particles onto the surface of GN and most of the Fe3O4 particles were deviated away from GN and aggregated to form larger units in pure ethanol. When used as anode for Li-ion batteries (LIBs), the Fe3O4@GN composite with a graphene content of 25 wt% synthesized in CO2–expanded ethanol manifested excellent charge–discharge cycling stability and rate performance compared with the sample synthesized in ethanol. Such improved electrochemical performances should be attributed to the intimate contact between the GN and Fe3O4 nanoparticles in the composite. Since the present method does not need tedious pre-treatment, surfactant, or precipitate, it is a green or sustainable technology and the solvents could be recycled easily after simple phase separation. This facile method can be extended to the synthesis of other metal oxide composites, which are expected to have good performance as anode materials for LIBs and other applications.

Encapsulation of metal oxide nanocrystals into porous carbon with ultrahigh performances in lithium-ion battery.

A simple and industrial scalable approach was developed to encapsulate metal oxide nanocrystals into porous carbon (PC) with a high distribution. With this method, the composite of PC-metal oxide were prepared in a large amount with a low cost; particularly they exhibit ultrahigh performances in lithium-ion battery applications. For example, the PC-CoOx and PC-FeOx show a high capacity around 1021 mA h g(-1) and 1200 mA h g(-1) at the current density of 100 mA g(-1) respectively, together with an excellent cycling ability (>400 cycles) and rate capacity even at the high current densities of 3 A g(-1) and 5 A g(-1).

CO2-assisted template synthesis of porous hollow bi-phase γ-/α-Fe2O3 nanoparticles with high sensor property

In this contribution, monodisperse porous hollow bi-phase γ-/α-Fe2O3 nanoparticles were successfully fabricated based on hard-template method with using carbon colloids as sacrificial templates. A new concept of assembling one kind of metal oxide with different crystalline structures into a single shell was presented for the first time. The critical procedure of coating carbon cores with a uniform layer of oxide was performed in CO2-expanded ethanol, which is a versatile way to produce high-quality hollow oxide nanoparticles. The formation of the novel bi-phase shell was achieved through combining the reduction ability of carbon cores under inert calcination atmosphere and the unique chemical composition of intermediate-shell formed in CO2-expanded ethanol. The porous hollow γ-/α-Fe2O3 nanoparticles with an average diameter of 99 nm not only possess combined properties of γ-Fe2O3 and α-Fe2O3, but also have a large specific surface area of 93.7 m2 g−1 and a high pore volume of 1.056 cm3 g−1, enabling them to have widespread applications in sensors, catalysis, magnetic and electrochemical areas, etc. Herein, such hollow bi-phase γ-/α-Fe2O3 nanoparticles were utilized to prepare a sensor device, and intriguingly it shows higher sensitivity and selectivity to ethanol than γ-Fe2O3 powders and many other porous α-Fe2O3 materials reported recently. The probable sensor mechanism of hollow γ-/α-Fe2O3 nanoparticles was discussed in detail.

Surfactant-assisted synthesis of Fe2O3 nanoparticles and F-doped carbon modification toward an improved Fe3O4@CFx/LiNi0.5Mn1.5O4 battery.

A simple surfactant-assisted reflux method was used in this study for the synthesis of cocklebur-shaped Fe2O3 nanoparticles (NPs). With this strategy, a series of nanostructured Fe2O3 NPs with a size distribution ranging from 20 to 120 nm and a tunable surface area were readily controlled by varying reflux temperature and the type of surfactant. Surfactants such as cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (F127) and sodium dodecyl benzenesulfonate (SDBS) were used to achieve large-scale synthesis of uniform Fe2O3 NPs with a relatively low cost. A new composite of Fe3O4@CFx was prepared by coating the primary Fe2O3 NPs with a layer of F-doped carbon (CFx) with a one-step carbonization process. The Fe3O4@CFx composite was utilized as the anode in a lithium ion battery and exhibited a high reversible capacity of 900 mAh g(-1) at a current density of 100 mA g(-1) over 100 cycles with 95% capacity retention. In addition, a new Fe3O4@CFx/LiNi(0.5)Mn(1.5)O4 battery with a high energy density of 371 Wh kg(-1) (vs cathode) was successfully assembled, and more than 300 cycles were easily completed with 66.8% capacity retention at 100 mA g(-1). Even cycled at the high temperature of 45 °C, this full cell also exhibited a relatively high capacity of 91.6 mAh g(-1) (vs cathode) at 100 mA g(-1) and retained 54.6% of its reversible capacity over 50 cycles. Introducing CFx chemicals to modify metal oxide anodes and/or any other cathode is of great interest for advanced energy storage and conversion devices.

Assembling metal oxide nanocrystals into dense, hollow, porous nanoparticles for lithium-ion and lithium–oxygen battery application

New dense hollow porous (DHP) metal oxide nanoparticles that are smaller than 100 nm and composed of Co3O4, FeOx, NiO and MnOx were prepared by densely assembling metal oxide nanocrystals based on the hard-template method using a carbon colloid as a sacrificial core. These nanoparticles are quite different from the traditional particles as their hollow interior originates from the stacking of nanocrystals rather than a spherical shell. The DHP nanoparticles preserve the intriguing properties of nanocrystals and possess desirable surface area and pore volume that enhance the active surface, which ultimately benefits applications such as lithium-ion batteries. The DHP Co3O4 nanoparticles demonstrated an enhanced capacity of 1168 mA h g(-1) at 100 mA g(-1)vs. 590 mA h g(-1) of powders and stable cycling performance greater than 250 cycles when used as an anode material. Most importantly, the electrochemical performance of DHP Co3O4 nanoparticles in a lithium-O2 battery was also investigated for the first time. A low charge potential of ∼4.0 V, a high discharge voltage near 2.74 V and a long cycle ability greater than 100 cycles at a delivered capacity of 2000 mA h g(-1) (current density, 200 mA g(-1)) were observed. The performances were considerably improved compared to recent results of mesoporous Co3O4, Co3O4 nanoparticles and a composite of Co3O4/RGO and Co3O4/Pd. Therefore, it would be promising to investigate such properties of DHP nanoparticles or other hollow metal (oxide) particles for the popular lithium-air battery.

Sodium salt effect on hydrothermal carbonization of biomass: a catalyst for carbon-based nanostructured materials for lithium-ion battery applications

The salt effect of NaxA (A = SO42−, Cl−, NO3−, etc.) on the hydrothermal carbonization of biomass is reported. It is a new catalyst and recyclable template to more simply and effectively prepare carbon-based materials, such as porous carbon-coated anode materials (e.g., Fe3O4@porous-C) in lithium-ion battery applications with enhanced performance.

Multilayer Approach for Advanced Hybrid Lithium Battery

Conventional intercalated rechargeable batteries have shown their capacity limit, and the development of an alternative battery system with higher capacity is strongly needed for sustainable electrical vehicles and hand-held devices. Herein, we introduce a feasible and scalable multilayer approach to fabricate a promising hybrid lithium battery with superior capacity and multivoltage plateaus. A sulfur-rich electrode (90 wt % S) is covered by a dual layer of graphite/Li4Ti5O12, where the active materials S and Li4Ti5O12 can both take part in redox reactions and thus deliver a high capacity of 572 mAh gcathode(-1) (vs the total mass of electrode) or 1866 mAh gs(-1) (vs the mass of sulfur) at 0.1C (with the definition of 1C = 1675 mA gs(-1)). The battery shows unique voltage platforms at 2.35 and 2.1 V, contributed from S, and 1.55 V from Li4Ti5O12. A high rate capability of 566 mAh gcathode(-1) at 0.25C and 376 mAh gcathode(-1) at 1C with durable cycle ability over 100 cycles can be achieved. Operando Raman and electron microscope analysis confirm that the graphite/Li4Ti5O12 layer slows the dissolution/migration of polysulfides, thereby giving rise to a higher sulfur utilization and a slower capacity decay. This advanced hybrid battery with a multilayer concept for marrying different voltage plateaus from various electrode materials opens a way of providing tunable capacity and multiple voltage platforms for energy device applications.