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.

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.

Suspensions of natural graphite particles were prepared in an aqueous medium using carboxymethyl cellulose ͑CMC͒ and emulsified styrene-butadiene copolymer latex as part of an environmentally friendly fabrication process for graphite anodes ͑negative electrodes͒ intended for application in Li-ion batteries. Suspensions were characterized by adsorption isotherms, electroacoustic measurements, rheology and sedimentation tests, at two different degrees of carboxymethyl substitution ͑DS͒ on CMC. A lower DS value ͑0.7͒ resulted in greater uptake of CMC on graphite compared with a higher DS value ͑1.28͒. This was attributed to attractive hydrophobic interactions associated with the lower carboxymethyl substitution. The greater adsorption for DS = 0.7 correlates with lower relative viscosity in concentrated graphite suspensions, a higher adhesion strength with a copper substrate, and a greater retention of discharge capacity after cycling. The effect of DS is attributed to differences in the aqueous dispersion properties and stability of graphite suspensions. Based on these results, we fabricated high-capacity graphite negative electrodes characterized by gravimetric and volumetric energy densities of greater than 340 mAh/g and 560 mAh/cm 3 , respectively. This formulation also led to improved adhesion strength, giving the as-fabricated cell an attractive cycle life greater than 90% of initial discharge capacity after 200 cycles.

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