Capacitive charge storage at an electrified interface investigated via direct first-principles simulations [Direct Simulation of Capacitive Charging of Graphene and Implications for Supercapacitor Design]

Radin, Maxwell D.; Ogitsu, Tadashi; Biener, Juergen; Otani, Minoru; Wood, Brandon C.

doi:10.1103/PhysRevB.91.125415

Capacitive charge storage at an electrified interface investigated via direct first-principles simulations [Direct Simulation of Capacitive Charging of Graphene and Implications for Supercapacitor Design]

Journal Article · Wed Mar 11 00:00:00 EDT 2015 · Physical Review. B, Condensed Matter and Materials Physics

DOI:https://doi.org/10.1103/PhysRevB.91.125415· OSTI ID:1325876

Radin, Maxwell D. ^[1]; Ogitsu, Tadashi ^[2]; Biener, Juergen ^[2]; Otani, Minoru ^[3]; Wood, Brandon C. ^[2]

Univ. of Michigan, Ann Arbor, MI (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
National Institute of Advanced Industrial Science and Technology, Tsukuba (Japan)

Understanding the impact of interfacial electric fields on electronic structure is crucial to improving the performance of materials in applications based on charged interfaces. Supercapacitors store energy directly in the strong interfacial field between a solid electrode and a liquid electrolyte; however, the complex interplay between the two is often poorly understood, particularly for emerging low-dimensional electrode materials that possess unconventional electronic structure. Typical descriptions tend to neglect the specific electrode-electrolyte interaction, approximating the intrinsic “quantum capacitance” of the electrode in terms of a fixed electronic density of states. Instead, we introduce a more accurate first-principles approach for directly simulating charge storage in model capacitors using the effective screening medium method, which implicitly accounts for the presence of the interfacial electric field. Applying this approach to graphene supercapacitor electrodes, we find that results differ significantly from the predictions of fixed-band models, leading to improved consistency with experimentally reported capacitive behavior. The differences are traced to two key factors: the inhomogeneous distribution of stored charge due to poor electronic screening and interfacial contributions from the specific interaction with the electrolyte. Lastly, our results are used to revise the conventional definition of quantum capacitance and to provide general strategies for improving electrochemical charge storage, particularly in graphene and similar low-dimensional materials.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1325876

Alternate ID(s):: OSTI ID: 1181178

Report Number(s):: LLNL-JRNL--659616

Journal Information:: Physical Review. B, Condensed Matter and Materials Physics, Journal Name: Physical Review. B, Condensed Matter and Materials Physics Journal Issue: 12 Vol. 91; ISSN 1098-0121; ISSN PRBMDO

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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