Abstract

Hybrid  supercapacitors  (SCs)  aim  to  combine  battery-like  energy  with  capacitor-like  power.  However,  progress  is  limited  by  electrode  designs  that  trade  capacity  for  slow  kinetics,  unstable  interfaces, and poor areal or volumetric performance. This review examines crystalline framework  electrodes, including metal-organic frameworks (MOFs) and covalent organic frameworks (COFs),  as well as framework-derived materials, which combine ordered porosity with programmable redox  chemistry. We develop a device-centered decision framework that links building-block chemistry  and  topology  to  charge-storage  mode,  ion  transport,  electrode  density,  and  dominant  failure  pathways  under  two-electrode  operation.  We  benchmark  MOFs,  COFs,  composites,  and  derived  phases across aqueous, organic, ionic-liquid, and gel electrolytes. We define minimum diagnostics  to distinguish double-layer capacitance, surface-redox pseudocapacitance, and battery-like behavior  in hybrid devices. To support translation from laboratory tests to practical electrodes, we synthesize  strategies  for  conductivity  and  stability,  including  percolation-network  design,  pore-access  engineering,  conformal  interface  stabilization,  and  controlled  reconstruction  or  derivatization,  thereby broadening operating windows while suppressing dissolution, pore flooding, and impedance  rise.  Finally,  we  map  degradation  modes  to  mitigation  levers  and  propose  a  fair-comparison  checklist that prioritizes realistic mass loading, electrode density, and areal and volumetric metrics,  enabling more durable, device-ready hybrid SCs.