Alloying Reaction Confinement Enables High-Capacity and Stable Anodes for Lithium-Ion Batteries

The current insertion anode chemistries are approaching their capacity limits; thus, alloying reaction anode materials with high theoretical specific capacity are investigated as potential alternatives for lithium-ion batteries. However, their performance is far from being satisfactory because of the large volume change and severe capacity decay that occurs upon lithium alloying and dealloying processes. To address these problems, we propose and demonstrate a versatile strategy that makes use of the electronic reaction confinement via the synthesis of ultrasmall Ge nanoparticles (10 nm) uniformly confined in a matrix of larger spherical carbon particles (Ge⊂C spheres). This architecture provides free pathways for electron transport and Li⁺ diffusion, allowing for the alloying reaction of the Ge nanoparticles. The thickness change of electrodes containing such a material, monitored byan in situ electrochemical dilatometer, is rather limited and reversible, confirming the excellent mechanical integrity of the confined electrode. As a result, these electrodes exhibit high reversible capacity (1310 mAh g^-1, 0.1C) and very impressive cycling ability (92% after 1000 cycles at 2C). A prototype device employing such an alloying electrode material in combination with LiNi_0.8Mn_0.1Co_0.1O₂ offers a high energy density of 250 Wh kg^-1.