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 particle's 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.

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