Lithium/fluorinated carbon (Li/CF x ) primary batteries have essential applications in consumer electronics and medical and high-power military devices. However, their application is limited due to the difficulty in achieving simultaneous high power density and high energy density in the CF x cathode. The tradeoff between conductivity and fluorine content is the decisive factor. Herein, by rational design, 3D porous fluorinated graphene microspheres (FGS-x) with both high conductivity and a high F/ C ratio are successfully synthesized for the first time. FGS-x possesses an F/C ratio as high as 1.03, a nanosheet structure with hierarchical pores, abundant CC bonds, few inactive C−F 2 bonds, and electrochemically active C−F bonds. The beneficial features that can increase discharge capacity, shorten the diffusion length for both ions and electrons, enhance the Li + intercalation kinetics, and accommodate the volume change are demonstrated. The Li/FGS-1.03 coin cell delivers an unprecedented power density of 71,180.9 W/kg at an ultrahigh rate of 50 C (43.25 A/g), coupled with a high energy density of 830.7 Wh/kg. Remarkably, the Li/FGS-1.03 pouch cell exhibits a record cell-level power density of 12,451.2 W/kg at 20 C. The in-depth investigation by the ex situ method on structural evolution at different discharge depths reveals that the excellent performance benefits from the structural stability and the uniform formation of LiF. The FGS-1.03 cathode also has excellent performance in extreme operating temperatures (0 to 100 °C) and high active material mass loading (4.3 mg/cm 2 ). These results indicate that the engineered fluorinated graphene developed here has great potential in applications requiring both high power density and high energy density.

Sodium and potassium are considered to be the most promising anode candidates due to their easy availability, low‐cost and similar chemical properties to lithium. Here, novel 3D accordion‐like fluorinated graphite nanosheets (FGNSs) are reported as cathodes for sodium primary batteries (SPBs) and potassium primary batteries (PPBs). The FGNSs‐x cathode exhibits unprecedented power and energy density due to the impressive 3D structure, high F/C ratio (1.0), and more surface CC bonds (7.14%). The FGNSs‐1.0 exhibits very high specific capacities of 831.3 and 834.1 mAh g−1 for SPBs and PPBs, respectively, close to the theoretical capacity. Besides, the maximum energy density of FGNSs‐1.0 in SPBs and PPBs are 1960.5 and 2144.6 Wh kg−1, respectively. The maximum power density for Na/CFx and K/CFx batteries could reach up to 7076.8 and 6227.4 W kg−1, respectively. The electrochemical performance of FGNSs‐1.0 at extreme temperatures (−30 to 100 °C), long storage time (60 days), high mass loading (3.6 mg cm−2), and pouch‐type cell is also evaluated for the first time. Surprisingly, FGNSs‐1.0 has outstanding performance in these projects. Therefore, the new‐type Na/CFx and K/CFx primary battery systems developed here have broad application prospects in high‐energy applications that require high‐power, low‐cost, and normal use under extreme conditions.

Fluorinated carbon (CFx) is considered as a promising cathode material for lithium/sodium/potassium primary batteries with superior theoretical energy density. However, achieving high energy and power densities simultaneously remains a considerable challenge due to the strong covalency of the C‐F bond in the highly fluorinated CFx. Herein, an efficient surface engineering strategy combining surface defluorination and nitrogen doping enables fluorinated graphene nanosheets (DFG‐N) to possess controllable conductive nanolayers and reasonably regulated C‐F bonds. The DFG‐N delivers an unprecedented dual performance for lithium primary batteries with a power density of 77456 W kg−1 and an energy density of 1067 Wh kg−1 at an ultrafast rate of 50 C, which is the highest level reported to date. The DFG‐N also achieved a record power density of 15256 and 17881 W kg−1 at 10 C for sodium and potassium primary batteries, respectively. The characterization results and density functional theory calculations demonstrate that the excellent performance of DFG‐N is attributed to surface engineering strategies that remarkably improve electronic and ionic conductivity without sacrificing the high fluorine content. This work provides a compelling strategy for developing advanced ultrafast primary batteries that combine ultrahigh energy density and power density.This article is protected by copyright. All rights reserved

The application of fluorinated carbon (CFx)-based lithium/sodium/potassium primary batteries (LPBs/SPBs/PPBs) with superior theoretical energy density in high-power devices remains limited due to the poor rate performance resulting from the low intrinsic conductivity of highly fluorinated CFx materials. Herein, novel nano-silver modified fluorinated carbon nanotubes (FCNTs@Ag-x) composites with high electrical conductivity were prepared without sacrificing the high fluorine content. The dual excellent performance achieved by the FCNTs@Ag-200 cathode is attributed to the three-dimensional conductive network synergistically constructed by the interlaced FCNTs and coated nano-Ag, together with electrochemically active C-F bonds co-regulated by Ag atoms and curvature, as well as abundant conductive semi-ionic C-F bonds and graphite-like sp2 C=C bonds, and few inactive C-F2 bonds. The FCNTs@Ag-200 cathode delivers very high energy densities of 2167, 1930, and 2150 Wh kg-1 for LPBs, SPBs, and PPBs, respectively, close to the theoretical energy density. The Li/FCNTs@Ag-200 battery exhibits an ultimate power density of up to 80501 W kg-1 at an ultrafast rate of 50 C and can withstand a pulse discharge of 150 C (~129.75 A g-1). Remarkably, unprecedented power densities of 36650 and 40672 W kg-1 are achieved at a record rate of 25 C using FCNTs@Ag-200 as the cathode for Na/CFx and K/CFx batteries, respectively, which is a significant improvement over the state-of-the-art. Therefore, the advanced CFx-based primary batteries developed here are promising in applications that simultaneously require fast discharge, high energy density, high power density, and long-term storage.