Triple-Confined Well-Dispersed Biactive NiCo₂S₄/Ni_0.96S on Graphene Aerogel for High-Efficiency Lithium Storage

Layered double hydroxides (LDHs), also known as hydrotalcite-like anionic clay compounds, have attracted increasing interest in electrochemical energy storage, in the main form of LDH precursor-derived transition metal oxides (TMOs). One typical approach to improve cycling stability of the LDH-derived TMOs is to introduce one- and two-dimensional conductive carbonaceous supports, such as carbon nanotubes and graphene. We herein demonstrate an effective approach to improve the electrochemical performances of well-dispersed biactive NiCo 2 S 4 /Ni 0.96 S as anode nanomaterials for lithium-ion batteries (LIBs), by introducing a three-dimensional graphene aerogel (3DGA) support. The resultant 3DGA supported NiCo 2 S 4 /Ni 0.96 S (3DGA/NCS) composite, obtained by sulfuration of NiCo-layered double hydroxide (NiCo-LDH) precursor in situ grown on the 3DGA support (3DGA/NiCo-LDH). Electrochemical tests show that the 3DGA/NCS composite indeed delivers the greatly enhanced electrochemical performances compared with the NiCo 2 S 4 /Ni 0.96 S counterpart on two-dimensional graphene aerogel, i.e., a high reversible capacity of 965 mA h g –1 after 200 cycles at 100 mA g –1 and especially a superlong cycling stability of 620 mA h g –1 after 800 cycles at 1 A g –1 . The enhancements could be ascribed to the compositional and structural advantages of boosting electrochemical performances: (i) well-dispersed NiCo 2 S 4 /Ni 0.96 S nanoparticles with interfacial nanodomains resulting from both the dual surface confinements of the 3DGA support and the crystallographic confinement of NiCo-well-arranged LDH crystalline layer, (ii) an appropriate specific surface area and a wide pore size distribution of mesopores and macropores, and (iii) highly conductive 3DGA support that is measured experimentally by using electrochemical impedance spectra to underlie the enhancement. Our results demonstrate that the tunable LDH precursor-derived synthesis route may be extended to prepare various transition metal sulfides and even transition metal phosphides for energy storage with the aid of tunable cationic type and molar ratio.