Structured Silicon Anodes for Lithium Battery Applications

Pillar arrays fabricated on silicon substrates have been tested as potential anodes for lithium batteries. Electrodes of array characteristics, diameter 580 ′ 150 nm: fractional surface coverage 0.34: height 810 nm are reported here. Cyclic voltammetry (CV) and cyclic galvanostatic tests of alloying/dealloying of electrochemically produced lithium with silicon were carried out, and results correlated with SEM studies. Aerial current densities in the low and fractional mA cm - 2 , and voltage 25 mV to 2 V (vs. L/Li + ) were used. CV features correspond to various Zintl phase compounds (ZPCs). Structured electrodes of Si pillars maintained their structural integrity throughout cycling; planar Si electrodes showed cracks (2 μm features) after 50 cycles. A model is advanced in which lithium diffuses through a layer of ZPC to react with Si: growing ZPCs plastically deforms where necessary. Upon lithium dealloying vacancies coalesce to form voids at the ZPC/Si interface, Si rejoins the substrate. or precipitates out as a nanocrystalline material, and the voids appear as a fine pattern of cracks, looking like dried mud. The extra surface area that a pillar structure can confer on Si electrodes is essential and makes it practical to consider the possible eventual use of such anodes in integrated battery structure;.

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