The role of catalysts and peroxide oxidation in lithium-oxygen batteries.

A promotor for lithium batteries: nanocrystalline cobalt(II,III) oxide supported on graphene enhances the transport kinetics for both oxygen reduction and oxygen evolution in the lithium-oxygen cell. On cycling the lithium-oxygen cell, the effect of the promoter is, however, eventually overwhelmed by side reactions in the cell, such as, the deposition of carbonates.

Screening for superoxide reactivity in Li-O2 batteries: effect on Li2O2/LiOH crystallization.

Unraveling the fundamentals of Li-O(2) battery chemistry is crucial to develop practical cells with energy densities that could approach their high theoretical values. We report here a straightforward chemical approach that probes the outcome of the superoxide O(2)(-), thought to initiate the electrochemical processes in the cell. We show that this serves as a good measure of electrolyte and binder stability. Superoxide readily dehydrofluorinates polyvinylidene to give byproducts that react with catalysts to produce LiOH. The Li(2)O(2) product morphology is a function of these factors and can affect Li-O(2) cell performance. This methodology is widely applicable as a probe of other potential cell components.

Conformational-induced doping effect of sodium dodecyl benzene sulfonate on single walled carbon nanotubes.

The doping behavior of single-walled carbon nanotubes (SWCNTs) was investigated with an emphasis on the control of the conformation of sodium dodecylbenzene sulfonate (NaDDBS) with sulfonate groups acting as an electro-withdrawing group. The conformation of adsorbed NaDDBS on SWCNTs was controlled as a function of the amount of NaDDBS. The doping behavior of SWCNTs was significantly affected by the dosing amount of NaDDBS due to the conformational change of NaDDBS adsorbed on the SWCNT surface, which affected the spatial distance between the SWCNT surface and the sulfonate groups in NaDDBS. At a higher concentration, the spatial distance between the sulfonate group in NaDDBS and SWCNT was not sufficiently close enough to dope SWCNT due to the repulsive forces between the sulfonate groups in NaDDBS. Alternatively, at a lower concentration, NaDDBS acted as a p-type dopant for SWCNTs. To this end, this paper demonstrates a new tendency of doping that is related to the adsorbed behavior of a dispersant.

Arrays of sealed silicon nanotubes as anodes for lithium ion batteries.

Silicon is a promising candidate for electrodes in lithium ion batteries due to its large theoretical energy density. Poor capacity retention, caused by pulverization of Si during cycling, frustrates its practical application. We have developed a nanostructured form of silicon, consisting of arrays of sealed, tubular geometries that is capable of accommodating large volume changes associated with lithiation in battery applications. Such electrodes exhibit high initial Coulombic efficiencies (i.e., >85%) and stable capacity-retention (>80% after 50 cycles), due to an unusual, underlying mechanics that is dominated by free surfaces. This physics is manifested by a strongly anisotropic expansion in which 400% volumetric increases are accomplished with only relatively small (<35%) changes in the axial dimension. These experimental results and associated theoretical mechanics models demonstrate the extent to which nanoscale engineering of electrode geometry can be used to advantage in the design of rechargeable batteries with highly reversible capacity and long-term cycle stability.

Dispersion properties of aqueous-based LiFePO4 pastes and their electrochemical performance for lithium batteries.

Aqueous-based LiFePO(4) pastes to fabricate the cathode of lithium-ion battery were investigated with an emphasis on chemical control of suspension component interactions among LiFePO(4) particulates, carbon black, carboxymethyl cellulose (CMC), and poly(acrylic acid) (PAA). The dispersion properties of LiFePO(4) were characterized using electroacoustic, flow behavior and green microstructural observation. Correlation was made between the dispersion properties and electrochemical performance of the particles. It was found that the addition of PAA significantly decreases the viscosity of the LiFePO(4) paste. The decrease of viscosity leads to increasing the solid concentration, which affects the electrochemical properties. The electrochemical characteristics of formulated pastes were evaluated using coin-type half cells. Although there is no significant difference between coin cells fabricated with CMC only and CMC/PAA combination in electrochemical cycling test, the dispersion properties of pastes indicate that the electrode fabricated with CMC/PAA, potentially, has much improved discharge capacity compared to that with CMC alone because of the possibility to increase active mass portion in electrode paste.

Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium­O2 batteries.

The lithium­O2 'semi-fuel' cell based on the reversible reaction of Li and O2 to form Li2O2 can theoretically provide energy densities that exceed those of Li-ion cells by up to a factor of five. A key limitation that differentiates it from other lithium batteries is that it requires effective catalysts (or 'promoters') to enable oxygen reduction and evolution. Here, we report the synthesis of a novel metallic mesoporous oxide using surfactant templating that shows promising catalytic activity and results in a cathode with a high reversible capacity of 10,000 mAh g(−1) (∼1,000 mAh g(−1) with respect to the total electrode weight including the peroxide product). This oxide also has a lower charge potential for oxygen evolution from Li2O2 than pure carbon. The properties are explained by the high fraction of surface defect active sites in the metallic oxide, and its unique morphology and variable oxygen stoichiometry. This strategy for creating porous metallic oxides may pave the way to new cathode architectures for the Li­O2 cell.

Si/Ge double-layered nanotube array as a lithium ion battery anode.

Problems related to tremendous volume changes associated with cycling and the low electron conductivity and ion diffusivity of Si represent major obstacles to its use in high-capacity anodes for lithium ion batteries. We have developed a group IVA based nanotube heterostructure array, consisting of a high-capacity Si inner layer and a highly conductive Ge outer layer, to yield both favorable mechanics and kinetics in battery applications. This type of Si/Ge double-layered nanotube array electrode exhibits improved electrochemical performances over the analogous homogeneous Si system, including stable capacity retention (85% after 50 cycles) and doubled capacity at a 3C rate. These results stem from reduced maximum hoop strain in the nanotubes, supported by theoretical mechanics modeling, and lowered activation energy barrier for Li diffusion. This electrode technology creates opportunities in the development of group IVA nanotube heterostructures for next generation lithium ion batteries.