Benjamin Hertzberg

High-performance lithium-ion anodes using a hierarchical bottom-up approach.

Si-based Li-ion battery anodes have recently received great attention, as they offer specific capacity an order of magnitude beyond that of conventional graphite. The applications of this transformative technology require synthesis routes capable of producing safe and easy-to-handle anode particles with low volume changes and stable performance during battery operation. Herein, we report a large-scale hierarchical bottom-up assembly route for the formation of Si on the nanoscale--containing rigid and robust spheres with irregular channels for rapid access of Li ions into the particle bulk. Large Si volume changes on Li insertion and extraction are accommodated by the particles internal porosity. Reversible capacities over five times higher than that of the state-of-the-art anodes (1,950 mA h g(-1)) and stable performance are attained. The synthesis process is simple, low-cost, safe and broadly applicable, providing new avenues for the rational engineering of electrode materials with enhanced conductivity and power.

A Major Constituent of Brown Algae for Use in High-Capacity Li-Ion Batteries

Alginate extracts help stabilize silicon nanoparticles used in a high-capacity lithium-silicon battery. The identification of similarities in the material requirements for applications of interest and those of living organisms provides opportunities to use renewable natural resources to develop better materials and design better devices. In our work, we harness this strategy to build high-capacity silicon (Si) nanopowder–based lithium (Li)–ion batteries with improved performance characteristics. Si offers more than one order of magnitude higher capacity than graphite, but it exhibits dramatic volume changes during electrochemical alloying and de-alloying with Li, which typically leads to rapid anode degradation. We show that mixing Si nanopowder with alginate, a natural polysaccharide extracted from brown algae, yields a stable battery anode possessing reversible capacity eight times higher than that of the state-of-the-art graphitic anodes.

Toward Efficient Binders for Li-Ion Battery Si-Based Anodes: Polyacrylic Acid

Si-based Li-ion battery anodes offer specific capacity an order of magnitude beyond that of conventional graphite. However, the formation of stable Si anodes is a challenge because of significant volume changes occurring during their electrochemical alloying and dealloying with Li. Binder selection and optimization may allow significant improvements in the stability of Si-based anodes. Most studies of Si anodes have involved the use of carboxymethylcellulose (CMC) and poly(vinylidene fluoride) (PVDF) binders. Herein, we show for the first time that pure poly(acrylic acid) (PAA), possessing certain mechanical properties comparable to those of CMC but containing a higher concentration of carboxylic functional groups, may offer superior performance as a binder for Si anodes. We further show the positive impact of carbon coating on the stability of the anode. The carbon-coated Si nanopowder anodes, tested between 0.01 and 1 V vs Li/Li+ and containing as little as 15 wt % of PAA, showed excellent stability during the first hundred cycles. The results obtained open new avenues to explore a novel series of binders from the polyvinyl acids (PVA) family.

Deformations in Si-Li anodes upon electrochemical alloying in nano-confined space.

The energy density of Li-ion batteries can be increased if graphitic anodes are replaced with nanostructured Si-based materials. Design of efficient Si anodes requires a better fundamental understanding of the possible changes in Si-Li alloy morphology during cycling. Here we propose a simple elastoplastic model to predict morphological changes in Si upon electrochemical reaction with Li in a confined geometry, such as a pore of a carbon nanotube (CNT). Our experiments with CNTs having inner Si coatings of different thicknesses confirmed the theoretical predictions and demonstrated irreversible shape changes in the first cycle and fully reversible shape changes in subsequent cycles. During the first lithiation, Si was found to adapt to the restricted shape of the rigid CNT pore and plastically deform during electrochemical alloying with Li. The sequential Li insertion and extraction periodically alters the tube size between the expanded and contracted states. The produced samples of porous Si with rigid CNT outer shell showed capacity up to 2100 mAh/g, stable performance for over 250 cycles, and outstanding average Coulombic efficiency in excess of 99.9%. CNT walls were demonstrated to withstand stresses caused by the initial Si expansion and Li intercalation.

N-Nitrosamines Formation from Secondary Amines by Nitrogen Fixation on the Surface of Activated Carbon

Our previous study demonstrated that many commercial activated carbon (AC) particles may catalyze transformation of secondary amines to yield trace levels of N-nitrosamines under ambient aerobic conditions. Because of the widespread usage of AC materials in numerous analytical and environmental applications, it is imperative to understand the reaction mechanism responsible for formation of nitrosamine on the surface of ACs to minimize their occurrence in water treatment systems and during analytical methods employing ACs. The study results show that the AC-catalyzed nitrosamine formation requires both atmospheric oxygen and nitrogen. ACs surface reactive sites react with molecular oxygen to form reactive oxygen species (ROS), which facilitate fixation of molecular nitrogen on the carbon surfaces to generate reactive nitrogen species (RNS) likely nitrous oxide and hydroxylamine that can react with adsorbed amines to form nitrosamines. ACs properties play a crucial role as more nitrosamine formation is associated with carbon surfaces with higher surface area, more surface defects, reduced surface properties, higher O(2) uptake capacity, and higher carbonyl group content. This study is a first of its kind on the nitrosamine formation mechanism involving nitrogen fixation on AC surfaces, and the information will be useful for minimization of nitrosamines in AC-based processes.