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Using Si as anode materials for Li-ion batteries remain challenging due to its morphological evolution and SEI modification upon cycling. The present work aims at developing a composite consisting of carbon-coated Si nanoparticles (Si@C NPs) intimately embedded in a three-dimensional (3D) graphene hydrogel (GHG) architecture to stabilize Si inside LiB electrodes. Instead of simply mixing both components, the novelty of the synthesis procedure lies in the in situ hydrothermal process, which was shown to successfully yield graphene oxide reduction, 3D graphene assembly production, and homogeneous distribution of Si@C NPs in the GHG matrix. Electrochemical characterizations in half-cells, on electrodes not containing additional conductive additive, revealed the importance of the protective C shell to achieve high specific capacity (up to 2200 mAh.g−1), along with good stability (200 cycles with an average Ceff > 99%). These performances are far superior to that of electrodes made with non-C-coated Si NPs or prepared by mixing both components. These observations highlight the synergetic effects of C shell on Si NPs, and of the single-step in situ preparation that enables the yield of a Si@C-GHG hybrid composite with physicochemical, structural, and morphological properties promoting sample conductivity and Li-ion diffusion pathways. [ABSTRACT FROM AUTHOR]

The interfacing of polyoxometalates and graphene can be considered to be an innovative way to generate hybrid structures that take advantage of the properties of both components. Polyoxometalates are redox-sensitive and photosensitive compounds with high temperature stability (up to 400 °C for some), showing tunable properties depending on the metal incorporated inside the complex. Graphene has a unique electronic band structure combined with good material properties for electrical and optical applications. The spontaneous, rather than electrochemical, functionalization of epitaxial graphene on SiC with Keggin phosphomolybdate derivative TBA3[PMo11O39{Sn(C6H4)CC(C6H4)N2}] (named KMoSn[N2+]) bearing a phenyl diazonium unit is investigated. Graphene decoration is evidenced by means of AFM, Raman, XPS, and cyclic voltammetry, indicating a successful immobilization of the polyoxomolybdate. The covalent bonding of the polyoxometalate to the graphene substrate can be deduced from the appearance of a D band in the Raman spectra and from the loss of mobility in the electrical conduction. High-resolution XPS spectra reveal an electron transfer from the graphene to the Mo complex. The comparison of charge-carrier density measurements before and after grafting supports the p-type doping effect, which is further evidenced by work function UPS measurements. [ABSTRACT FROM AUTHOR]