Although graphite materials with desirable comprehensive properties dominate the anode market of commercial lithium‐ion batteries (LIBs), their low capacity during fast charging precludes further commercialization. In the present work, natural graphite (G) is reported not only to suffer from low capacity during fast charging, but also from charge failure after many charging cycles. Using different characterization techniques, severe graphite exfoliation, and continuously increasing solid electrolyte interphase (SEI) are demonstrated as reasons for the failure of G samples. An ultrathin artificial SEI is proposed, addressing these problems effectively and ensuring extremely stable operation of the graphite anode, with a capacity retention of ≈97.5% after 400 cycles at 1 C. Such an artificial SEI modification strategy provides a universal approach to tailoring and designing better anode materials for next‐generation LIBs with high energy densities.

graphite materials). [3] Both spinel-type (LiMn 2 O 4 , ≈120 mAh g -1 ) and polyaniontype (LiFePO 4 , ≈150 mAh g -1 ) materials can take full advantage of the transition metal redox (one-electron transfer), whereas the large molecular mass limits their specific capacity. [4] Layered materials, such as LiCoO 2 , can only partially utilize transition metal redox (less than one-electron transfer), as high-voltage charging causes severe structural deterioration. [5] Although nascent nickelrich cathodes (≈200 mAh g -1 ), such as LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) and LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA), possess decent capacity by increasing the nickel content as the nickel redox can occur at a relatively low potential, there is little potential to further improve their capacity. [6] The LRCs, usually expressed as a Li 2 MnO 3 •LiNi x Co y Mn z O 2 (x + y + z = 1) formula, possesses a superior specific capacity (> 250 mAh g -1 ) among cathode materials, owing to its cationic redox (LiNi x Co y Mn z O 2 part at relatively low potential, <4.5 V versus Li/Li + ) and anionic redox (Li 2 MnO 3 part at high potential, 4.5-4.8 V). [7] Nevertheless, LRCs also present serious challenges, including high voltage hysteresis and low coulombic efficiency in the first cycle, high capacity and voltage fading during cycling, and poor rate performance. [8][9][10][11][12] These problems primarily occur from irreversible Lithium-rich cathodes (LRCs) show great potential to improve the energy density of commercial lithium-ion batteries owing to their cationic and anionic redox characteristics. Herein, a complete conductive network using carbon nanotubes (CNTs) additives to improve the poor kinetics of LRCs is fabricated. Ex situ X-ray photoelectron spectroscopy first demonstrates that the slope at a low potential and the following long platform can be assigned to the transition metal and oxygen redox, respectively. The combination of galvanostatic intermittent titration technique and electrochemical impedance spectroscopy further reveal that a battery with CNTs exhibited accelerated kinetics, especially for the O-redox process. Consequently, LRCs with CNTs exhibit a much better rate and cycling performance (≈89% capacity retention at 2 C for over 200 cycles) than the Super P case. Eventually, TEM results imply that the improved electrochemical performance of the CNTs case also benefits from its more stable bulk and surface structures. Such a facile conductive additive modification strategy also provides a universal approach for the enhancement of the electron diffusion properties of other electrode materials.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smtd.202200449.