Low specific capacitances and/or limited working potential (≤4.5 V). of the prevalent carbon-based positive electrodes as the inborn bottleneck seriously hinder practical advancement of lithium-ion capacitors. Thus, breakthroughs in enhancement of both specific capacitances and upper cutoff potentials are enormously significant for high-energy density lithium-ion capacitors. Herein, we first meticulously design and scalably fabricate a commercializable fluorine-doped porous carbon material with competitive tap density, large active surface, appropriate aperture distribution, and promoted affinity with the electrolyte, rendering its abundant electroactive inter-/surface and rapid PF₆^- transport. Theoretical calculations authenticate that fluorine-doped porous carbon possesses lower PF₆^- adsorption energy and stronger interaction with PF₆^-. Thanks to the remarkable structural/compositional superiority, when served as a positive electrode toward lithium-ion capacitors, the commercial-level fluorine-doped porous carbon showcases the record-breaking electrochemical properties within a wider working window of 2.5–5.0 V (vs Li/Li⁺) in terms of high-rate specific capacitances and long-duration stability, much superior to commercial activated carbon. More significantly, the 4.5 V-class graphite//fluorine-doped porous carbon lithium-ion capacitors are first constructed and manifest competitive electrochemical behaviors with long-cycle life, modest polarization, and large energy density. Our work provides a commendable positive paradigm and contributes a major step forward in next-generation lithium-ion capacitors and even other high-energy density metal-ion capacitors.

Metal-ion capacitors (including Li⁺, Na⁺, and K⁺) effectively combine a battery negative electrode capable of reversibly intercalating metal cations, together with an electrical double-layer positive electrode. However, such novel cell design has a birth defect, namely kinetics mismatch between sluggish negative electrode and fast positive electrode, thus limiting the energy-power performance. Herein, we design a MoS₂-carbon composite anode with the ordered macroporous architecture and interlayer-expanded feature, exhibiting the fast and reversible Na⁺ redox processes. This kinetically favored anode is coupled with a homemade activated carbon cathode that allows for the excellent electrochemical performance of sodium-ion capacitor with respect to large specific capacity, high-rate capability, and robust cycling. Through quantification of the potential swings of anode and cathode via a three-electrode Swagelok cell, we for the first time observe the abnormal variation law of potential swings and thus directly providing the evidence that the kinetics gap has been filled up by this kinetically favored anode. Our results represent a crucial step toward understanding the key issues of kinetics mismatch for hybrid cell, thus propelling the development of design of kinetically favored anode materials for high-performance metal-ion capacitors.