  Downsizing well-established materials to the nanoscale is a key route to
novel functionalities, in particular if different functionalities are merged in
hybrid nanomaterials. Hybrid carbon-based hierarchical nanostructures are
particularly promising for electrochemical energy storage since they combine
benefits of nanosize effects, enhanced electrical conductivity and integrity of
bulk materials. We show that endohedral multiwalled carbon nanotubes (CNT)
encapsulating high-capacity (here: conversion and alloying) electrode materials
have a high potential for use in anode materials for lithium-ion batteries
(LIB). There are two essential characteristics of filled CNT relevant for
application in electrochemical energy storage: (1) rigid hollow cavities of the
CNT provide upper limits for nanoparticles in their inner cavities which are
both separated from the fillings of other CNT and protected against
degradation. In particular, the CNT shells resist strong volume changes of
encapsulates in response to electrochemical cycling, which in conventional
conversion and alloying materials hinders application in energy storage
devices. (2) Carbon mantles ensure electrical contact to the active material as
they are unaffected by potential cracks of the encapsulate and form a stable
conductive network in the electrode compound. Our studies confirm that
encapsulates are electrochemically active and can achieve full theoretical
reversible capacity. The results imply that encapsulating nanostructures inside
CNT can provide a route to new high-performance nanocomposite anode materials
for LIB.
