4.8 Article

Oxygen Vacancies Lead to Loss of Domain Order, Particle Fracture, and Rapid Capacity Fade in Lithium Manganospinel (LiMn2O4) Batteries

期刊

ACS APPLIED MATERIALS & INTERFACES
卷 6, 期 14, 页码 10849-10857

出版社

AMER CHEMICAL SOC
DOI: 10.1021/am500671e

关键词

neutron diffraction; point defects; Li-ion batteries; mechanical degradation; electron microscopy; energy storage

资金

  1. National Science Foundation [DMR-1253347]
  2. General Motors/University of Michigan Advanced Battery Coalition for Drivetrains
  3. NSF [DMR-0320710, DMR-0315633]
  4. Direct For Mathematical & Physical Scien [1253347] Funding Source: National Science Foundation
  5. Division Of Materials Research [1253347] Funding Source: National Science Foundation

向作者/读者索取更多资源

Spinel-structured lithium manganese oxide (LiMn2O4) has attracted much attention because of its high energy density, low cost, and environmental impact. In this article, structural analysis methods such as powder neutron diffraction (PND), X-ray diffraction (XRD), and high-resolution transmission and scanning electron microscopies (TEM & SEM) reveal the capacity fading mechanism of LiMn2O4 as it relates to the mechanical degradation of the material. Micro-fractures form after the first charge (to 4.45 V vs. Li+/0) of a commercial lithium manganese oxide phase, best represented by the formula LiMn2O3.88. Diffraction methods show that the grain size decreases and multiple phases form after 850 electrochemical cycles at 0.2 C current. The microfractures are directly observed through microscopy studies as particle cracks propagate along the (1 1 1) planes, with clear lattice twisting observed along this direction. Long-term galvanostatic cycling results in increased charge-transfer resistance and capacity loss. Upon preparing samples with controlled oxygen contents, LiMn2O4.03 and LiMn2O3.87, the mechanical failure of the lithium manganese oxide can be correlated to the oxygen vacancies in the materials, providing guidance for better synthesis methods.

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