Deconvolving double-layer, pseudocapacitance, and battery-like charge-storage mechanisms in nanoscale LiMn2O4 at 3D carbon architectures. (10th June 2018)

• Record Type: Journal Article
• Authors: Ko, Jesse S.; Sassin, Megan B.; Rolison, Debra R.; Long, Jeffrey W.
• Is Part Of: Electrochimica acta. Volume 275(2018)
• Page Start: 225
• Page End: 235
• Publication Date: 2018-06-10
• Subjects: Pseudocapacitance -- Double-layer -- Impedance -- Voltammetry -- Manganese oxide -- Lithium spinel -- Nanostructured; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2018.04.149
• Languages: English
• ISSNs: 0013-4686

Abstract

Abstract: Lithium manganese spinel, LiMn2 O4 (LMO), is a well-established active material for batteries, in which charge is stored via a two-stage insertion of Li + that manifests with coupled current peaks or voltage plateaus under voltammetric or galvanostatic conditions, respectively. The charge–discharge kinetics for LMO are significantly enhanced when the oxide is expressed in a nanoscale form, for example as an ultrathin coating of nanocrystallites at the surfaces of a 3D carbon substrate, such as fiber paper–supported carbon nanofoams (CNFs). In addition to expressing well-defined "battery-like" Li + -insertion peaks between ∼0.6 and 1 V vs . Ag/AgCl when cycled in aqueous lithium sulfate, LMO@CNF electrodes exhibit a pseudocapacitance envelop at more negative potentials (∼0.2–0.6 V). The pseudocapacitive character of LMO@CNF is further verified when cycled in aqueous sodium sulfate, where a broad capacitance envelop dominates the voltammetric response over the entire potential range at a current density an order of magnitude greater than expected for double-layer capacitance. Thus, the LMO@CNF electrode provides a prime example where multiple distinct charge-storage mechanisms are expressed in a single material. Herein, we apply voltammetry and impedance-based methods to deconvolve the respective contributions of double-layer capacitance, surface-based pseudocapacitance, and battery-like Li + insertion. The use of power-law analysis provides a general assignment of transport dynamics, while projecting impedance data as 3D Bode-style representations provides key mechanistic information regarding the time/frequency–potential response of LMO@CNF electrodes. Graphical abstract: Highlights: Nanocrystalline LiMn2 O4 @3D-carbon exhibits both pseudocapacitive- and battery-like Li + insertion charge-storage behavior. Power-law analyses indicate surface-based reactions with pseudocapacitance and finite diffusion for battery-like behavior. Impedance data expressed as 3D Bode plots maps charge-storage dynamics onto the electrode potential plane.