Block copolymer derived 3-D interpenetrating multifunctional gyroidal nanohybrids for electrical energy storage

Abstract

Multifunctional three-dimensional (3-D) nano-architectures, integrating all device components within tens of nanometers, offer great promise for next generation electrical energy storage applications, but have remained challenging to achieve. The lack of appropriate synthesis methods, enabling precise 3-D spatial control at the nanoscale, remains a key issue holding back the development of such intricate architectures. Here we present an approach to such systems based on the bottom-up synthesis of penta-continuous nanohybrid monoliths with four functional components integrated in a triblock terpolymer derived core-shell double gyroid architecture. Two distinct 3-D interpenetrating networks serving as cathode and current collector are separated from a carbon anode matrix by continuous, ultrathin polymer electrolyte shells. All periodically ordered domains are less than 20 nm in their layer dimensions and integrated throughout the macroscopic monolith. Initial electrochemical measurements with the Li-ion/S system exhibit reversible batterylike charge-discharge characteristics with orders of magnitude decreases in footprint area over conventional flat thin layer designs.Nanostructured materials have dramatically impacted fundamental and applied research as well as applications due to their unique properties arising from well-defined spatial confinement and large surface area-to-volume ratios 1-3 . Co-continuous nanohybrids of multiple distinct functional materials offer the potential for great advances in catalysis, energy conversion, and optical devices due to their large interfacial areas combined with three-dimensional (3-D) continuity of all phases 4-6 . While developments in top-down photolithographic techniques and materials have enabled access to ever decreasing feature sizes in two-and three-dimensional (2-D and 3-D) architectures for transistors and other circuit elements 7,8 , leading to widespread deployment of electronics 9 , rapid 3-D nanohybrid device formation remains challenging and

Thick Electrode Batteries: Principles, Opportunities, and Challenges

“…Moreover, the confinement effect of the 3D current collector pore structure also enables a shortened and relatively homogeneous charge transfer pathway through the electrode, which is critical for achieving a good rate performance for thick electrode. In the past few years, a series of integrated electrodes with excellent mechanical strength and electrochemical performance have been demonstrated with architectures based on diverse 3D conductive scaffolds such as graphite foam, graphene foam, nickel foam, copper foam, alloy foam, polymer‐derived carbon framework, and so on.…”

MXene-based 3D porous macrostructures for electrochemical energy storage

“…However, these are usually limited to planar geometries and micrometric scales. 3D designs such as the 3D tri-continuous electrode assembly as proposed by Werner et al [103] allows the integration of the nanometric components in a 3D architecture improving their power capability without negatively impacting the energy density.…”

Gyroidal Niobium Sulfide/Carbon Hybrid Monoliths for Electrochemical Energy Storage

“…Subsequent sulfidation in hydrogen and sulfurcontaining atmosphere yielded an ordered TMD with a simultaneously formed carbon shell. [17] The electrochemical properties of NbS 2 were investigated by the Goodenough group, but only lithium insertion was observed, [18] whereas lithium conversion reactions with increased capacities have only been demonstrated for transition metal-and selenium-doped NbS 2 nanosheets. Few-layered NbS 2 nanocrystals are engulfed in a microporous carbon shell to provide structural and mechanical integrity as well as electrical conductivity.…”

“…[13] Here, we introduce a three-dimensional, monolithic niobium disulfide/carbon hybrid material with a gyroidal microstructure synthesized via macromolecular co-assembly of a tailored block copolymer and an organometallic niobium precursor. [17] The electrochemical properties of NbS 2 were investigated by the Goodenough group, but only lithium insertion was observed, [18] whereas lithium conversion reactions with increased capacities have only been demonstrated for transition metal-and selenium-doped NbS 2 nanosheets. It is the first report on a gyroidal TMD/carbon hybrid material in literature.…”

“…[16] The attractiveness of such gyroidal electrode materials was further underlined by the recent demonstration of an ordered, threedimensional battery by the Wiesner group. [17] The electrochemical properties of NbS 2 were investigated by the Goodenough group, but only lithium insertion was observed, [18] whereas lithium conversion reactions with increased capacities have only been demonstrated for transition metal-and selenium-doped NbS 2 nanosheets. [19] Our material shows, to the best of our knowledge, the first stable lithium conversion chemistry for monolithic NbS 2 which we link to the high exposure of active sites from the gyroidal structure and the stability and electrical conductivity provided by the porous carbon shell.…”