Investigation on the Voltage Hysteresis of Mn₃O₄ for Lithium-Ion Battery Applications

Abstract

In lithium-ion batteries (LIBs), conversion-based electrodes such as transition-metal oxides and sulfides exhibit promising characteristics including high capacity and long cycle life. However, the main challenge for conversion electrodes to be industrialized remains on voltage hysteresis. In this study, Mn3O4 powder was used as an anode material for LIBs to investigate the root cause of the hysteresis. First, the electrochemical reaction paths were found to be dominated by Mn/Mn2+ redox couple after the first lithiation from galvanostatic charging/discharging (GCD) and cyclic voltammetry (CV) measurements. Then, the voltage hysteresis was proposed to be composed of reaction overpotential (∼0.373 V) and intrinsic overpotential (∼0.377 V), which were related to the diffusion behaviors according to CV, galvanostatic intermittent titration technique (GITT), and electrochemical impedance spectroscopy (EIS) analyses. Furthermore, results revealed that the formation of disparate phase distribution during lithiation and delithiation could be the root cause of the intrinsic overpotential of Mn3O4. These results were based on ultrahigh-resolution transmission electron microscopy (UHRTEM) and molecular dynamics (MD) simulation. It was expected that improving the diffusion behaviors of the systems could eliminate the voltage hysteresis of Mn3O4. In summary, this paper provides an explicit insight into the hysteresis for conversion-based Mn3O4 that could also be applied to other oxide systems and very crucial to reduce energy loss for commercializing oxides as anode materials in LIBs.

Engineering Hierarchical Co@N-Doped Carbon Nanotubes/α-Ni(OH)2 Heterostructures on Carbon Cloth Enabling High-Performance Aqueous Nickel–Zinc Batteries

“…Lithium-ion batteries (LIBs) have attracted tremendous research efforts because of their extraordinary energy density, excellent rechargeability, and environmental friendliness. Unfortunately, the drawbacks including deficient lithium resources, being costly, and safety problems severely block their further application. − In contrast, aqueous rechargeable batteries have stimulated extensive research attention in terms of their high safety and moderate price. , Among them, aqueous nickel–zinc (Ni–Zn) batteries have stimulated particular research enthusiasms in view of the following merits: (1) aqueous Ni–Zn batteries possess a higher operating voltage (∼1.8 V) when compared with other aqueous batteries; (2) metallic Zn exhibits a relatively high capacity of 820 mAh g –1 and also has other merits such being low cost, environmentally friendly, and steady in aqueous electrolyte and having a low equilibrium potential; , (3) aqueous electrolyte has a higher ionic conductivity than organic electrolytes, which usually shows much enhanced rate performance. , Unfortunately, the applications of aqueous Ni–Zn batteries are greatly restricted by the inferior energy density and poor cycling durability.…”

Rational design of 3D net-like carbon based Mn3O4 anode materials with enhanced lithium storage performance

“…The first CV curve is distinctly distinguished from those in the successive cycles, suggesting that the reaction mechanism is different in the initial lithiation, which has already been observed in the previously reported Mn 3 O 4 based electrodes. 36 The Mn 3 O 4 /CP anode undergoing a series of electrochemical reactions can be explicated by the following equations: 37,38 Mn 3 O 4 + Li + + e À -LiMn 3 O 4…”

“…The first CV curve is distinctly distinguished from those in the successive cycles, suggesting that the reaction mechanism is different in the initial lithiation, which has already been observed in the previously reported Mn 3 O 4 based electrodes. 36 The Mn 3 O 4 /CP anode undergoing a series of electrochemical reactions can be explicated by the following equations: 37,38 Mn 3 O 4 + Li + + e − → LiMn 3 O 4 LiMn 3 O 4 + Li + + e − → Li 2 O + 3MnOMnO x + 2 x Li + + 2 x e − ↔ x Li 2 O + Mn ( x = 1–1.5)A broad reduction peak around 1.69 V in the first scan is assigned to the intercalation of Li + ions into Mn 3 O 4 (eqn (1)). The peak at 1.46 V can be attributed to the conversion to MnO (eqn (2)).…”

Confining Nano-GeP in Nitrogenous Hollow Carbon Fibers toward Flexible and High-Performance Lithium-Ion Batteries

“…The semidiameter for GeP@NC- x was less than 100 Ω, indicating that the diffusion resistance of Li + in GeP@NC- x was very small. The GITT curves of GeP@NC- x are further shown in Figure b, and the lithium-ion diffusion coefficient ( D Li + ) can be calculated based on the following equation: , where D Li+ is the Li + diffusion coefficient (cm 2 s –1 ), τ is the time of the current pulse (s), V m is the molar volume (cm 3 mol –1 ), m B is the mass loading (g), M B is the molecular weight (g mol –1 ), and S is the contact surface area between the electrode and the electrolyte (cm 2 ). D Li+ curves calculated according to GITT profiles are shown in Figure c.…”