Romil Bhandavat

MoS2/graphene composite paper for sodium-ion battery electrodes.

We study the synthesis and electrochemical and mechanical performance of layered free-standing papers composed of acid-exfoliated few-layer molybdenum disulfide (MoS2) and reduced graphene oxide (rGO) flakes for use as a self-standing flexible electrode in sodium-ion batteries. Synthesis was achieved through vacuum filtration of homogeneous dispersions consisting of varying weight percent of acid-treated MoS2 flakes in GO in DI water, followed by thermal reduction at elevated temperatures. The electrochemical performance of the crumpled composite paper (at 4 mg cm(-2)) was evaluated as counter electrode against pure Na foil in a half-cell configuration. The electrode showed good Na cycling ability with a stable charge capacity of approximately 230 mAh g(-1) with respect to total weight of the electrode with Coulombic efficiency reaching approximately 99%. In addition, static uniaxial tensile tests performed on crumpled composite papers showed high average strain to failure reaching approximately 2%.

Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries.

Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm−2) delivers a charge capacity of ∼588 mAh g−1electrode (∼393 mAh cm−3electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries.

Polymer-Derived Ceramic Functionalized MoS2 Composite Paper as a Stable Lithium-Ion Battery Electrode.

A facile process is demonstrated for the synthesis of layered SiCN-MoS2 structure via pyrolysis of polysilazane functionalized MoS2 flakes. The layered morphology and polymer to ceramic transformation on MoS2 surfaces was confirmed by use of electron microscopy and spectroscopic techniques. Tested as thick film electrode in a Li-ion battery half-cell, SiCN-MoS2 showed the classical three-stage reaction with improved cycling stability and capacity retention than neat MoS2. Contribution of conversion reaction of Li/MoS2 system on overall capacity was marginally affected by the presence of SiCN while Li-irreversibility arising from electrolyte decomposition was greatly suppressed. This is understood as one of the reasons for decreased first cycle loss and increased capacity retention. SiCN-MoS2 in the form of self-supporting paper electrode (at 6 mg·cm−2) exhibited even better performance, regaining initial charge capacity of approximately 530 mAh·g−1 when the current density returned to 100 mA·g−1 after continuous cycling at 2400 mA·g−1 (192 mAh·g−1). MoS2 cycled electrode showed mud-cracks and film delamination whereas SiCN-MoS2 electrodes were intact and covered with a uniform solid electrolyte interphase coating. Taken together, our results suggest that molecular level interfacing with precursor–derived SiCN is an effective strategy for suppressing the metal-sulfide/electrolyte degradation reaction at low discharge potentials.

Very high laser-damage threshold of polymer-derived Si(B)CN-carbon nanotube composite coatings.

We study the laser irradiance behavior and resulting structural evolution of polymer-derived silicon-boron-carbonitride (Si(B)CN) functionalized multiwall carbon nanotube (MWCNT) composite spray coatings on copper substrate. We report a damage threshold value of 15 kWcm(-2) and an optical absorbance of 0.97 after irradiation. This is an order of magnitude improvement over MWCNT (1.4 kWcm(-2), 0.76), SWCNT (0.8 kWcm(-2), 0.65) and carbon paint (0.1 kWcm(-2), 0.87) coatings previously tested at 10.6 μm (2.5 kW CO2 laser) exposure. Electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy suggests partial oxidation of Si(B)CN forming a stable protective SiO2 phase upon irradiation.

Improved Electrochemical Capacity of Precursor-Derived Si(B)CN-Carbon Nanotube Composite as Li-Ion Battery Anode

We study the electrochemical behavior of precursor-derived siliconboron carbonitride (Si(B)CN) ceramic and Si(B)CN coated-multiwalled carbon nanotube (CNT) composite as a lithium-ion battery anode. Reversible capacity of Si(B)CN was observed to be 138 mA h/g after 30 cycles, which is four times that of SiCN (~25 mA h/g) processed under similar conditions, while the Si(B)CN-CNT composite showed further enhancement demonstrating 412 mA h/g after 30 cycles. Improved performance of Si(B)CN is attributed to the presence of boron that is known to modify SiCNs nanodomain structure resulting in improved chemical stability and electronic conductivity. Post-cycling microscopy and chemical analysis of the anode revealed formation of a stable passivating layer, which resulted in stable cycling.

Synthesis of polymer-derived ceramic Si(B)CN-carbon nanotube composite by microwave-induced interfacial polarization.

We demonstrate synthesis of a polymer-derived ceramic (PDC)-multiwall carbon nanotube (MWCNT) composite using microwave irradiation at 2.45 GHz. The process takes about 10 min of microwave irradiation for the polymer-to-ceramic conversion. The successful conversion of polymer coated carbon nanotubes to ceramic composite is chemically ascertained by Fourier transform-infrared and X-ray photoelectron spectroscopy and physically by thermogravimetric analysis and transmission electron microscopy characterization. Frequency dependent dielectric measurements in the S-Band (300 MHz to 3 GHz) were studied to quantify the extent of microwave-CNT interaction and the degree of selective heating available at the MWCNT-polymer interface. Experimentally obtained return loss of the incident microwaves in the specimen explains the reason for heat generation. The temperature-dependent permittivity of polar molecules further strengthens the argument of internal heat generation.

Synthesis of Graphene Films by Rapid Heating and Quenching at Ambient Pressures and Their Electrochemical Characterization

We study the process of graphene growth on Cu and Ni substrates subjected to rapid heating (approximately 8 °C/s) and cooling cycles (approximately 10 °C/s) in a modified atmospheric pressure chemical vapor deposition furnace. Electron microscopy followed by Raman spectroscopy demonstrated successful synthesis of large-area few-layer graphene (FLG) films on both Cu and Ni substrates. The overall synthesis time was less than 30 min. Further, the as-synthesized films were directly utilized as anode material and their electrochemical behavior was studied in a lithium half-cell configuration. FLG on Cu (Cu-G) showed reduced lithium-intercalation capacity when compared with SLG, BLG and Bare-Cu suggesting its substrate protective nature (barrier to Li-ions). Although graphene films on Ni (Ni-G) showed better Li-cycling ability similar to that of other carbons suggesting that the presence of graphene edge planes (typical of Ni-G) is important in effective uptake and release of Li-ions in these materials.