Daohao Sim

Olivine-Type Nanosheets for Lithium Ion Battery Cathodes

Olivine-type LiMPO4 (M = Fe, Mn, Co, Ni) has become of great interest as cathodes for next-generation high-power lithium-ion batteries. Nevertheless, this family of compounds suffers from poor electronic conductivities and sluggish lithium diffusion in the [010] direction. Here, we develop a liquid-phase exfoliation approach combined with a solvothermal lithiation process in high-pressure high-temperature (HPHT) supercritical fluids for the fabrication of ultrathin LiMPO4 nanosheets (thickness: 3.7-4.6 nm) with exposed (010) surface facets. Importantly, the HPHT solvothermal lithiation could produce monodisperse nanosheets while the traditional high-temperature calcination, which is necessary for cathode materials based on high-quality crystals, leads the formation of large grains and aggregation of the nanosheets. The as-synthesized nanosheets have features of high contact area with the electrolyte and fast lithium transport (time diffusion constant in at the microsecond level). The estimated diffusion time for Li(+) to diffuse over a [010]-thickness of <5 nm (L) was calculated to be less than 25, 2.5, and 250 μs for LiFePO4, LiMnPO4, and LiCoPO4 nanosheets, respectively, via the equation of t = L(2)/D. These values are about 5 orders of magnitude lower than the corresponding bulk materials. This results in high energy densities and excellent rate capabilities (e.g., 18 kW kg(-1) and 90 Wh kg(-1) at a 80 C rate for LiFePO4 nanosheets).

Flexible carbon nanotube papers with improved thermoelectric properties

Although theoretical calculations indicate that the thermoelectric figure of merit, ZT, of carbon nanotubes (CNTs) could reach >2, the experimentally reported ZT values of CNTs are typically in the range of 10−3–10−2, which is not attractive for thermal energy conversion applications. In this work, we report the preparation of flexible CNT bulky paper for thermoelectric applications. The ZT values of the CNT bulky papers could be significantly enhanced by Ar plasma treatment, i.e. increasing it from 0.01 for pristine CNTs to 0.4 for Ar-plasma treated CNTs. The improved thermoelectric properties were mainly due to the greatly increased Seebeck coefficients and a reduction in the thermal conductivities, although the electrical conductivities also decreased. Such an improvement makes the plasma treated CNT bulky papers promising as a new type of thermoelectric material for certain niche applications as they are easily processed, mechanically flexible and durable, and chemically stable.

Facile preparation of hydrated vanadium pentoxide nanobelts based bulky paper as flexible binder-free cathodes for high-performance lithium ion batteries

Hydrated vanadium pentoxide (V2O5·0.44H2O, HVO) nanobelts were synthesized by a simply high-yield (e.g. up to ∼99%) hydrothermal approach. The length of these nanobelts was up to several hundred micrometers while the diameter was only ∼20 nm and the thickness was ∼10 nm. Binder-free bulky papers were prepared by using these HVO nanobelts and were tested as Li ion battery cathodes. The unique architecture of the HVO bulky paper provides hierarchical porous channels and large specific surface area, which facilitate fast ion diffusion and effectively strain relaxation upon charge-discharge cycling. The electrochemical tests revealed that the flexible HVO cathode could deliver high reversible specific capacities with ∼100% Coulombic efficiency, especially at high C rates. For example, it achieved a reversible capacity of 163 mAh g−1 at 6.8 C.

One-pot synthesis of carbon-coated VO2(B) nanobelts for high-rate lithium storage

Uniform carbon-coated single crystalline vanadium dioxide (VO2(B)@C) nanobelts were successfully prepared by using a facile one-pot hydrothermal approach. Sucrose plays a dual role in this hydrothermal process, namely as a carbon precursor for the carbon shell and, as a reductant to reduce V2O5 to VO2(B). The thickness of the carbon coating layer is tunable from 3.0 to 6.9 nm by changing the ratio of the precursors. Although a high carbon content can improve the electrical conductivity of VO2(B)@C nanobelts, a thick carbon coating layer would block the lithium ion diffusion. The optimal thickness is found to be 4.3 nm (carbon content: 6.6 wt%), where the cathode displays superior performance with highly reversible specific capacities, good cycling stabilities and excellent rate capabilities (e.g. 100 mA h g−1 at 12.4 C).

Facile Preparation of Ordered Porous Graphene–Metal Oxide@C Binder‐Free Electrodes with High Li Storage Performance

A facile and general method is reported to prepare ordered porous graphene-based binder-free electrodes on a large scale. This preparation process allows the easy adjustment of the selected components, weight ratio of componets, and the thickness of the electrodes. Such ordered porous electrodes demonstrate superior Li storage properties; for example, graphene-Fe3 O4 @C depicts high capacities of 1123.8 and 505 mAh g(-1) at current densities of 0.5 and 10 A g(-1) , respectively.

Synthesis of hexagonal-symmetry α-iron oxyhydroxide crystals using reduced graphene oxide as a surfactant and their Li storage properties

Microcrystalline α-iron oxyhydroxide/reduced graphene oxide (α-FeOOH/rGO) samples have been successfully synthesized by a facile hydrothermal process. The α-FeOOH/rGO samples are either hexagonal disks with a diameter of ∼1 μm and a thickness of 300 nm or hexapods with a diameter of ∼2 μm and a thickness of 700 nm, while only bulk and aggregated FeOOH is observed without the addition of graphene oxide sheets. The size and shape of the α-FeOOH depend on the reaction time, concentration of Fe3+, and the addition of graphene oxide. The growth of the hexagonal disks and hexapods is mainly due to a series of phase and structural transformations. The α-FeOOH/rGO displays superior anode performance with a high reversible specific capacity of 569 mA h g−1 at the 50th cycle.

Controlled CVD growth of Cu-Sb alloy nanostructures.

Sb based alloy nanostructures have attracted much attention due to their many promising applications, e.g. as battery electrodes, thermoelectric materials and magnetic semiconductors. In many cases, these applications require controlled growth of Sb based alloys with desired sizes and shapes to achieve enhanced performance. Here, we report a flexible catalyst-free chemical vapor deposition (CVD) process to prepare Cu-Sb nanostructures with tunable shapes (e.g. nanowires and nanoparticles) by transporting Sb vapor to react with copper foils, which also serve as the substrate. By simply controlling the substrate temperature and distance, various Sb-Cu alloy nanostructures, e.g. Cu(11)Sb(3) nanowires (NWs), Cu(2)Sb nanoparticles (NPs), or pure Sb nanoplates, were obtained. We also found that the growth of Cu(11)Sb(3) NWs in such a catalyst-free CVD process was dependent on the substrate surface roughness. For example, smooth Cu foils could not lead to the growth of Cu(11)Sb(3) nanowires while roughening these smooth Cu foils with rough sand papers could result in the growth of Cu(11)Sb(3) nanowires. The effects of gas flow rate on the size and morphology of the Cu-Sb alloy nanostructures were also investigated. Such a flexible growth strategy could be of practical interest as the growth of some Sb based alloy nanostructures by CVD may not be easy due to the large difference between the condensation temperature of Sb and the other element, e.g. Cu or Co.