Highly Reversible Conversion Anodes Composed of Ultralarge Monolithic Grains with Seamless Intragranular Binder and...

Conversion anodes enable a high capacity for lithium-ion batteries due to more than one electron transfer. However, the collapse of the host structure during cycling would cause huge volume expansion and phase separation, leading to the degradation and disconnection of the mixed conductive network of the electrode. The initial nanostructuring and loose spatial distribution of active species are often resorted to in order to alleviate the evolution of the electrode morphology, but at the cost of the decrease of grain packing density. The utilization of ultralarge microsized grains of high density as the conversion anode is still highly challenging. Here, a proof-of-concept grain architecture characterized by endogenetic binder matrix and wiring network is proposed to guarantee the structural integrity of monolithic grains as large as 50-100 μm during deep conversion reaction. Such big grains were fabricated by self-assembly and pyrolysis of a Keggin-type polyoxometalate-based complex with protonated tris[2-(2-methoxyethoxy)-ethyl]amine (TDA-1-H⁺). The metal-organic precursor can guarantee the firm adherence of numerous Mo-O clusters and nuclei into a highly elastic monolithic structure without evident grain boundaries and intergranular voids. The pyrolyzed TDA-1-H⁺ not only serves as in situ binder and conductive wire to glue adjacent Mo-O moieties but also acts as a Li-ion pathway to promote sufficient lithiation on surrounding Mo-O. Such a monolithic electrode design leads to an unusual high-conversion-capacity performance (1000 mAh/g) with satisfactory reversibility (reaching at least 750 cycles at 1 A/g). These cycled grains are not disassembled even after undergoing long-term cycling. The conception of the intragranular binder is further confirmed by consolidating the MoO₂ porous network after in situ stuffing of MoS₂ nanobinders.