Kirkendall Growth of Hollow Mn₃O₄ Nanoparticles upon Galvanic Reaction of MnO with Cu²⁺ and Evaluation as Anode for Lithium-Ion Batteries

Abstract

We report the formation of high surface area hollow Mn 3 O 4 nanoparticles that form as a result of the galvanic reaction of Cu 2+ with MnO nanocrystals concomitant with a nanoscale Kirkendall effect. The MnO nanocrystals were prepared according to the ultralarge scale synthesis reported by Hyeon, which allowed the preparation of hollow Mn 3 O 4 in multigram quantities. Ex-situ analyses with transmission electron microscopy and powder X-ray diffraction show the morphology and phase stability of the hollow particles correlate with DSC-TGA data and show collapse of the hollow particles at temperatures greater than 200 °C. Electrodes fabricated from hollow Mn 3 O 4 exhibited excellent initial Li ion storage capability (initial discharge capacity = 1324 mAh/g) but poor cycling performance (97% loss of discharge capacity after 10th cycle), whereas Mn 3 O 4 -MWCNT electrodes exhibited good reversibility and discharge capacity of 760 mAh/g after 100 cycles.

In Situ Synthesis of Mn3O4 Nanoparticles on Hollow Carbon Nanofiber as High‐Performance Lithium‐Ion Battery Anode

“…There are two slopes in the first charging curve. The first slope between 1.2 and 1.8 V mainly results from the oxidation of Mn to MnO, and the second slope, ranging from 1.9 to 2.2 V, is due to the oxidation of MnO to Mn 3 O 4 . In subsequent cycles, the discharge plateau changed to 0.4 V, which indicated structural rearrangement.…”

“…The first slope between 1.2 and 1.8 Vm ainly results from the oxidation of Mn to MnO, and the second slope, ranging from 1.9t o 2.2 V, is due to the oxidation of MnO to Mn 3 O 4 . [49] In subsequentc ycles, the discharge plateau changed to 0.4V ,w hich indicated structural rearrangement. From the 2nd to 100th cycle, the voltage profiles were almostu nchanged, which illustrated superior cycling stability.T he above results are in good agreement with the CV curves.…”

Controllable synthesis of nanostructured metal oxide and oxyhydroxide materials via electrochemical methods

“…[71,72] The formation of hollow structures via the Kirkendall effect has attracted substantial attention. [73][74][75] Many different hollow nano-forms including rattles, boxes, bowls, spheres, and particles of various shapes have been reported using GRR; Figure 3C The GRR has been also employed in the preparation of exfoliated 2D layered metal oxide nanosheets. The authors reported the galvanic replacement reaction of exfoliated MnO 2 nanosheets by Fe 2+ or Sn 2+ ions resulting in highly anisotropic Fe or Sn oxide nanosheets.…”

High power and stable P-doped yolk-shell structured Si@C anode simultaneously enhancing conductivity and Li+ diffusion kinetics

“…Lithium-ion battery (LIB) featuring high capacity, light weight and long life, is an significant energy storage device [1][2][3][4]. Many materials (such as Li metal [5,6], Si [7], SnSe x [8], Mn3O4 [9], ReS2 [10]) can be used as the negative electrodes of LIBs. Li metal anode has been extensively studied owing to the high theoretical capacity, low density, and low redox potential [11].…”