Mechanochemical Synthesis of Mn₃O₄ Nanocrystals and Their Lithium Intercalation Capability

Abstract

Syntheses of Mn 3 O 4 involve either high sintering temperatures to produce well crystallized products or the use of water-soluble precursors, surfactants, and organic solvents to generate nanocrystalline products. Mechanochemical approaches are known to be effective in the preparation of fine-grained or nanoscaled materials, while also being environmentally friendly because no solvents and no sintering at high temperatures are required. We report the solvent free mechanochemical synthesis of Mn 3 O 4 nanocrystals at room temperature, from a mixture of MnO and Mn 2 O 3 . The single-phase product was characterized by Rietveld refinement and SEM images. The obtained crystallite size was 14.2(2) nm, which is among the smallest ever produced crystallite sizes of Mn 3 O 4 . The obtained product reveals an enormous increase in lithium intercalation capability, which was proven via chemical lithium intercalation at room temperature. More than 50% lithiation of nanocrystalline Mn 3 O 4 is observed after a reaction time of 1 h, while coarse-grained material from a solid-state reaction shows no intercalation under the same reaction conditions. Therefore, the produced manganese oxide has a high potential in lithium battery applications.

Structural Stability and Properties of Marokite-Type γ-Mn3O4

“…Synthetic manganese oxides and manganese oxide minerals play an important role in different technological processes and applications. , For example, some of them are utilized as effective catalysts, − as supercapacitors, as ferroelectrics or multiferroics, − as elements in ion batteries, − as semiconductors, and for many other purposes. − In general, manganese oxides, including Mn-based perovskites, − are inexpensive and highly functional materials, which combine interesting electronic and magnetic properties and, therefore, have remained in the focus of recent investigations.…”

Low-Temperature Catalytic Methane Deep Oxidation over Sol-gel derived Mesoporous Hausmannite (Mn3O4) Spherical Particles

“…1a, the hkl reflections at (112), ( 200), ( 103), ( 121), (004), ( 220), ( 105 structure (space group I41/amd). [24,25] From the XRD spectrum, no peaks characteristics of impurities were detected, attesting of the purity of the sample. The standard grains size estimated from the XRD was ~17 nm.…”

Cobalt Nanocluster-Decorated N-Rich Hierarchical Carbon Architectures Efficiently Catalyze Oxygen Reduction and Hydrogen Evolution Reactions

“…39−41 It is worth mentioning that mechanochemical synthesis (solvent-free grinding) could induce the formation of nanocrystals, abundant defects, and full mixing of different components. 42,43 Moreover, mechanochemical synthesis based on solid phase mixing should be helpful for loading more metal ions into the systems. When mechanochemical synthesis was applied to crystalline Q [6] and cobalt salt, the formation of assemblies with hierarchical nanostructures and large amounts of cobalt ions can be expected.…”

“…Because of its uniform pore size and unique structure, Q[6] has attracted increased interest in gas storage, absorption, , and supramolecular chemistry . In addition, it can be a catalyst support for making many metal electrocatalysts with improved performance , and energy storage. − It is worth mentioning that mechanochemical synthesis (solvent-free grinding) could induce the formation of nanocrystals, abundant defects, and full mixing of different components. , Moreover, mechanochemical synthesis based on solid phase mixing should be helpful for loading more metal ions into the systems. When mechanochemical synthesis was applied to crystalline Q[6] and cobalt salt, the formation of assemblies with hierarchical nanostructures and large amounts of cobalt ions can be expected.…”