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From in situ transmission electron microscopy (TEM) observations, we present direct evidence of lithium-assisted welding between physically contacted silicon nanowires (SiNWs) induced by electrochemical lithiation and delithiation. This electrochemical weld between two SiNWs demonstrates facile transport of lithium ions and electrons across the interface. From our in situ observations, we estimate the shear strength of the welded region after delithiation to be approximately 200 MPa, indicating that a strong bond is formed at the junction of two SiNWs. This welding phenomenon could help address the issue of capacity fade in nanostructured silicon battery electrodes, which is typically caused by fracture and detachment of active materials from the current collector. The process could provide for more robust battery performance either through self-healing of fractured components that remain in contact or through the formation of a multiconnected network architecture., (© 2012 American Chemical Society)

Rechargeable, all-solid-state Li ion batteries (LIBs) with high specific capacity and small footprint are highly desirable to power an emerging class of miniature, autonomous microsystems that operate without a hardwire for power or communications. A variety of three-dimensional (3D) LIB architectures that maximize areal energy density has been proposed to address this need. The success of all of these designs depends on an ultrathin, conformal electrolyte layer to electrically isolate the anode and cathode while allowing Li ions to pass through. However, we find that a substantial reduction in the electrolyte thickness, into the nanometer regime, can lead to rapid self-discharge of the battery even when the electrolyte layer is conformal and pinhole free. We demonstrate this by fabricating individual, solid-state nanowire core-multishell LIBs (NWLIBs) and cycling these inside a transmission electron microscope. For nanobatteries with the thinnest electrolyte, ≈110 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. With electrolyte thickness increased to 180 nm, the self-discharge rate is reduced substantially, and the NWLIBs maintain a potential above 2 V for over 2 h. Analysis of the nanobatteries' electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes directly through the electrolyte. Our study illustrates that, at these nanoscale dimensions, the increased electric field can lead to large electronic current in the electrolyte, effectively shorting the battery. The scaling of this phenomenon provides useful guidelines for the future design of 3D LIBs., (© 2011 American Chemical Society)