Supercapacitors suffer from lack of energy density and impulse the energy density limit, so a new class of hybrid electrode materials with promising architectures is strongly desirable. Here, the rational design of a 3D hierarchical sandwich Co S /α-MnS@N-C@MoS nanowire architecture is achieved during the hydrothermal sulphurization reaction by the conversion of binary mesoporous metal oxide core to corresponding individual metal sulphides core along with the formation of outer metal sulphide shell at the same time. Benefiting from the 3D hierarchical sandwich architecture, Co S /α-MnS@N-C@MoS electrode exhibits enhanced electrochemical performance with high specific capacity/capacitance of 306 mA h g /1938 F g at 1 A g , and excellent cycling stability with a specific capacity retention of 86.9% after 10 000 cycles at 10 A g . Moreover, the fabricated asymmetric supercapacitor device using Co S /α-MnS@N-C@MoS as the positive electrode and nitrogen doped graphene as the negative electrode demonstrates high energy density of 64.2 Wh kg at 729.2 W kg , and a promising energy density of 23.5 Wh kg is still attained at a high power density of 11 300 W kg . The hybrid electrode with 3D hierarchical sandwich architecture promotes enhanced energy density with excellent cyclic stability for energy storage.

By changing the mixed metal sulfide composition, morphology tuning of an active electrode material can be possible, which can have a huge impact on its electrochemical performance. Here, effective morphology tuning of Ni−Co layered double hydroxide (LDH)/MMoS x (M = Co, Ni, and Zn) heteronanostructures is demonstrated by varying the composition of MMoS x . Taking advantage of the benefits associated with Kirkendall growth and Ostwald ripening, tunable morphologies were successfully achieved. Among the Ni−Co LDH/MMoS x (M = Co, Ni, and Zn) heteronanostructures, a Ni−Co LDH/NiMoS x core−shell structured electrode delivered a high specific capacity of 404 mAh g −1 at 3 mA cm −2 and an extraordinary cycling stability (after 10 000 cycles) of 93.2% at 50 mA cm −2 . In addition, an asymmetric supercapacitor (ASC) device coupled with Ni−Co LDH/ NiMoS x as the cathode and Fe 2 O 3 /reduced graphene oxide as the anode exhibited excellent cell capacity and extraordinary cycling stability. Moreover, the ASC device provided a very high specific energy of 72.6 Wh kg −1 at a specific power of 522.7 W kg −1 and maintained the specific power of 23.5 Wh kg −1 at 5357.6 W kg −1 , demonstrating its high applicability to energy storage devices.

A thin layer of N–C sandwiched between an electroactive MnCo2O4 core and MnO2 shell results in sophisticated, robust core@sandwich@shell as a highly efficient energy storage material.