Stabilizing Effect of Polycrystalline Diamond on Graphite Anodes for Li Ion Batteries

Improving the interfacial stability of graphite anodes remains a major challenge for extending the lifetime of lithium-ion batteries. In this study, ultrananocrystalline diamond (UNCD) and nitrogen-incorporated UNCD (N-UNCD) coatings were employed as protective layers to enhance the electrochemical and mechanical robustness of graphite electrodes. Half-cells were cycled for 60 charge–discharge cycles, and their behavior was examined through electrochemical impedance spectroscopy (EIS), Distribution of Relaxation Times (DRT), and Equivalent Circuit Modeling (ECM) to disentangle the characteristic relaxation processes. The potential–capacity profiles exhibited the typical LiC12–LiC6 transition plateaus without any additional features for the coated electrodes, confirming that the UNCD and N-UNCD films do not participate in lithium storage but serve as chemically inert and electrically stable interlayers. In contrast, the uncoated reference graphite anodes showed greater capacity fluctuations and increasing interfacial impedance. DRT and ECM analyses revealed four consistent relaxation processes—electronic transport (τ1), ionic transport through the electrolyte (τ2), Solid Electrolyte Interface (SEI) response (τ3), and lithium intercalation (τ4). The τ2 process remained invariant, whereas τ3 and τ4 were markedly stabilized by the UNCD and N-UNCD coatings. UNCD exhibited the lowest SEI-related resistance and the most stable charge-transfer kinetics, while N-UNCD displayed an initially higher τ3 resistance followed by progressive self-stabilization after 20 charge/discharge cycles, linked to reorganization of nitrogen-rich grain boundaries. Overall, polycrystalline diamond coatings—particularly UNCD—proved to be highly effective in suppressing SEI layer growth, minimizing impedance rise, and preserving lithium intercalation efficiency, leading to enhanced long-term electrochemical performance. These findings highlight the potential of diamond-based protective layers as a durable and scalable strategy for next-generation graphite anodes.