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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Unveiling the Mechanism of Mn Dissolution Through a Dynamic Cathode‐Electrolyte Interphase on LiMn2O4

Abstract Understanding the formation and evolution of the cathode‐electrolyte interphase (CEI), which forms at the interface between the cathode and electrolyte, is crucial for revealing degradation mechanisms in cathode materials, especially for developing strategies to stabilize the interphase in the strongly oxidizing conditions that evolve at high operating voltages in next‐generation Li‐ion batteries. However, The present understanding of the CEI is challenged by its complex and dynamic nature. In this work, near‐edge X‐ray absorption fine structure spectroscopy, electrochemical characterization, and reactive molecular dynamics simulations are combined to reveal a mechanism for CEI formation and evolution above model LiMn 2 O 4 (LMO) thin‐film electrodes in contact with conventional carbonate‐based electrolytes. It is found that Mn dissolution from LMO can be understood in terms of repetitive Mn 3 O 4 formation and dissolution behavior during cycling, which is closely connected to electrolyte decomposition and a key aspect of the CEI formation and growth. The behavior of the CEI in this model system offers detailed insight into the dynamic chemistry of the interphase, underscoring the important role of electrolyte composition and cathode surface structure in interphase degradation.

Ou, Wenhan↗
DOE OSTI2022

Correlating wavelength dependence in LiMn2O4 cathode photo-accelerated fast charging with deformations in local structure

The growth in electrified transportation has benefited from the massive worldwide research efforts used to discover and improve electrode materials and electrolytes. Nevertheless, lithium-ion batteries still suffer from a slow-charging limitation. Recently, it has been demonstrated that white light illumination of LiMn2O4 provokes faster charging, improving the kinetics of delithiation without the use of nanostructured active materials. In this work, we probe the mechanism of photo-accelerated fast charging and show that Mn d-d electronic transitions occurring under red light illumination are largely responsible for the increased charging rate. It is further demonstrated through X-ray absorption spectroscopy methods that LiMn2O4 Mn-Mn bond distances shorten after d-electron excitation. The shrinkage in the crystal volume beneficially contributes to delithiation kinetics by lowering the resistance to lithium-ion conduction. Advanced materials that can absorb light to modulate their structure may provide us with a new mechanistic pathway to pursue for increasing charge transfer rates.

25 ENERGY STORAGE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

LiMn2O4 is Spinel-like structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eighteen inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–65°. There are two shorter (1.97 Å) and two longer (2.07 Å) Li–O bond lengths. In the second Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–65°. There are two shorter (1.98 Å) and two longer (2.07 Å) Li–O bond lengths. In the third Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–64°. There are a spread of Li–O bond distances ranging from 1.98–2.02 Å. In the fourth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–64°. There are a spread of Li–O bond distances ranging from 1.98–2.02 Å. In the fifth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Li–O bond distances ranging from 1.97–2.02 Å. In the sixth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–65°. There are a spread of Li–O bond distances ranging from 2.01–2.08 Å. In the seventh Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–64°. There are two shorter (2.00 Å) and two longer (2.08 Å) Li–O bond lengths. In the eighth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–63°. There is three shorter (1.97 Å) and one longer (1.98 Å) Li–O bond length. In the ninth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–65°. There are a spread of Li–O bond distances ranging from 1.98–2.08 Å. In the tenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–64°. There are a spread of Li–O bond distances ranging from 2.00–2.08 Å. In the eleventh Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–64°. There are a spread of Li–O bond distances ranging from 2.01–2.08 Å. In the twelfth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Li–O bond distances ranging from 1.98–2.02 Å. In the thirteenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Li–O bond distances ranging from 1.98–2.02 Å. In the fourteenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 55–65°. There are two shorter (1.97 Å) and two longer (2.07 Å) Li–O bond lengths. In the fifteenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–64°. There are a spread of Li–O bond distances ranging from 1.98–2.02 Å. In the sixteenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–64°. There are a spread of Li–O bond distances ranging from 1.98–2.02 Å. In the seventeenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 54–62°. All Li–O bond lengths are 1.97 Å. In the eighteenth Li1+ site, Li1+ is bonded to four O2- atoms to form LiO4 tetrahedra that share corners with twelve MnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–63°. There are a spread of Li–O bond distances ranging from 1.98–2.02 Å. There are thirty-six inequivalent Mn+3.50+ sites. In the first Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.98 Å. In the second Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.16 Å. In the third Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.16 Å. In the fourth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.91–1.99 Å. In the fifth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.98 Å. In the sixth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.91–1.99 Å. In the seventh Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.15 Å. In the eighth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.99 Å. In the ninth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–2.14 Å. In the tenth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.15 Å. In the eleventh Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.15 Å. In the twelfth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.99 Å. In the thirteenth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.98 Å. In the fourteenth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.91–1.99 Å. In the fifteenth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.15 Å. In the sixteenth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.99 Å. In the seventeenth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.98 Å. In the eighteenth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.97–2.21 Å. In the nineteenth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.91–1.99 Å. In the twentieth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.13 Å. In the twenty-first Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.12 Å. In the twenty-second Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.14 Å. In the twenty-third Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–2.14 Å. In the twenty-fourth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.98–2.22 Å. In the twenty-fifth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.12 Å. In the twenty-sixth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.98–2.21 Å. In the twenty-seventh Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.98–2.21 Å. In the twenty-eighth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.92–2.15 Å. In the twenty-ninth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.91–1.99 Å. In the thirtieth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six LiO4 tetrahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.91–1.99 Å. In

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

LiMn2O4 crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with five MnO6 octahedra, an edgeedge with one LiO6 octahedra, edges with five MnO6 octahedra, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–47°. There are a spread of Li–O bond distances ranging from 1.96–2.27 Å. In the second Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.90–2.46 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with five MnO6 octahedra, an edgeedge with one LiO6 octahedra, edges with five MnO6 octahedra, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–51°. There are a spread of Li–O bond distances ranging from 1.97–2.22 Å. There are six inequivalent Mn+3.50+ sites. In the first Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form distorted MnO6 octahedra that share corners with two equivalent LiO6 octahedra, corners with eight MnO6 octahedra, edges with two equivalent MnO6 octahedra, and a faceface with one LiO6 octahedra. The corner-sharing octahedra tilt angles range from 49–53°. There are a spread of Mn–O bond distances ranging from 1.95–2.46 Å. In the second Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent LiO6 octahedra, corners with eight MnO6 octahedra, edges with two equivalent MnO6 octahedra, and a faceface with one LiO6 octahedra. The corner-sharing octahedra tilt angles range from 46–54°. There are a spread of Mn–O bond distances ranging from 1.94–2.25 Å. In the third Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO6 octahedra, edges with three LiO6 octahedra, and edges with four MnO6 octahedra. The corner-sharing octahedra tilt angles range from 50–54°. There are a spread of Mn–O bond distances ranging from 1.91–2.01 Å. In the fourth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three equivalent LiO6 octahedra, corners with four MnO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with four MnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–53°. There are a spread of Mn–O bond distances ranging from 1.90–2.03 Å. In the fifth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO6 octahedra, edges with three LiO6 octahedra, and edges with four MnO6 octahedra. The corner-sharing octahedra tilt angles range from 51–53°. There are a spread of Mn–O bond distances ranging from 1.91–2.15 Å. In the sixth Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three equivalent LiO6 octahedra, corners with four MnO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with four MnO6 octahedra. The corner-sharing octahedra tilt angles range from 7–52°. There are a spread of Mn–O bond distances ranging from 1.89–2.08 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+ and three Mn+3.50+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with two OLi2Mn3 square pyramids, corners with two equivalent OLi2Mn3 trigonal bipyramids, corners with two OLiMn3 trigonal pyramids, an edgeedge with one OLi3Mn3 octahedra, and an edgeedge with one OLiMn3 trigonal pyramid. In the second O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Mn+3.50+ atoms. In the third O2- site, O2- is bonded in a 5-coordinate geometry to two Li1+ and three Mn+3.50+ atoms. In the fourth O2- site, O2- is bonded in a 5-coordinate geometry to two Li1+ and three Mn+3.50+ atoms. In the fifth O2- site, O2- is bonded to one Li1+ and three Mn+3.50+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with three equivalent OLi3Mn3 octahedra, corners with two OLiMn3 trigonal pyramids, edges with two OLi2Mn3 square pyramids, an edgeedge with one OLi2Mn3 trigonal bipyramid, and an edgeedge with one OLiMn3 trigonal pyramid. The corner-sharing octahedra tilt angles range from 9–12°. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.50+ atoms. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to one Li1+ and three Mn+3.50+ atoms. In the eighth O2- site, O2- is bonded to one Li1+ and three Mn+3.50+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with three equivalent OLi2Mn3 trigonal bipyramids, corners with two OLiMn3 trigonal pyramids, an edgeedge with one OLi3Mn3 octahedra, and edges with two OLi2Mn3 square pyramids. In the ninth O2- site, O2- is bonded to two Li1+ and three Mn+3.50+ atoms to form OLi2Mn3 square pyramids that share a cornercorner with one OLi2Mn3 square pyramid, a cornercorner with one OLi2Mn3 trigonal bipyramid, a cornercorner with one OLiMn3 trigonal pyramid, edges with two equivalent OLi3Mn3 octahedra, an edgeedge with one OLi2Mn3 square pyramid, an edgeedge with one OLi2Mn3 trigonal bipyramid, and edges with two OLiMn3 trigonal pyramids. In the tenth O2- site, O2- is bonded to three Li1+ and three Mn+3.50+ atoms to form OLi3Mn3 octahedra that share corners with three equivalent OLiMn3 trigonal pyramids, edges with four OLi2Mn3 square pyramids, edges with two equivalent OLi2Mn3 trigonal bipyramids, and edges with two OLiMn3 trigonal pyramids. In the eleventh O2- site, O2- is bonded to two Li1+ and three Mn+3.50+ atoms to form distorted OLi2Mn3 trigonal bipyramids that share corners with two OLi2Mn3 square pyramids, corners with five OLiMn3 trigonal pyramids, edges with two equivalent OLi3Mn3 octahedra, edges with two OLi2Mn3 square pyramids, and an edgeedge with one OLiMn3 trigonal pyramid. In the twelfth O2- site, O2- is bonded to two Li1+ and three Mn+3.50+ atoms to form OLi2Mn3 square pyramids that share a cornercorner with one OLi2Mn3 square pyramid, a cornercorner with one OLi2Mn3 trigonal bipyramid, a cornercorner with one OLiMn3 trigonal pyramid, edges with two equivalent OLi3Mn3 octahedra, an edgeedge with one OLi2Mn3 square pyramid, an edgeedge with one OLi2Mn3 trigonal bipyramid, and edges with two OLiMn3 trigonal pyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

LiMn2O4 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six equivalent MnO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 10–14°. There are two shorter (2.14 Å) and four longer (2.18 Å) Li–O bond lengths. There are two inequivalent Mn+3.50+ sites. In the first Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share edges with four equivalent LiO6 octahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.91–1.97 Å. In the second Mn+3.50+ site, Mn+3.50+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with six equivalent LiO6 octahedra, edges with two equivalent LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 10–14°. There are a spread of Mn–O bond distances ranging from 1.95–2.24 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded to two equivalent Li1+ and three Mn+3.50+ atoms to form a mixture of edge and corner-sharing OLi2Mn3 square pyramids. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn+3.50+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

LiMn2O4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a 1-coordinate geometry to three O2- atoms. There are a spread of Li–O bond distances ranging from 1.69–2.00 Å. In the second Li1+ site, Li1+ is bonded in a 1-coordinate geometry to one Mn+3.50+ and three O2- atoms. The Li–Mn bond length is 2.28 Å. There are a spread of Li–O bond distances ranging from 1.63–2.14 Å. In the third Li1+ site, Li1+ is bonded in a 1-coordinate geometry to one Mn+3.50+ and three O2- atoms. The Li–Mn bond length is 2.29 Å. There are a spread of Li–O bond distances ranging from 1.62–1.99 Å. In the fourth Li1+ site, Li1+ is bonded in a 3-coordinate geometry to three O2- atoms. There are a spread of Li–O bond distances ranging from 1.76–2.00 Å. In the fifth Li1+ site, Li1+ is bonded in a 1-coordinate geometry to one Mn+3.50+ and three O2- atoms. The Li–Mn bond length is 2.27 Å. There are a spread of Li–O bond distances ranging from 1.63–2.18 Å. In the sixth Li1+ site, Li1+ is bonded in a 1-coordinate geometry to one Mn+3.50+ and three O2- atoms. The Li–Mn bond length is 2.30 Å. There are a spread of Li–O bond distances ranging from 1.69–2.00 Å. There are twelve inequivalent Mn+3.50+ sites. In the first Mn+3.50+ site, Mn+3.50+ is bonded in a 2-coordinate geometry to four O2- atoms. There are a spread of Mn–O bond distances ranging from 2.00–2.26 Å. In the second Mn+3.50+ site, Mn+3.50+ is bonded in a distorted hexagonal bipyramidal geometry to two Li1+ and six O2- atoms. There are a spread of Mn–O bond distances ranging from 1.98–2.45 Å. In the third Mn+3.50+ site, Mn+3.50+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 1.92–2.39 Å. In the fourth Mn+3.50+ site, Mn+3.50+ is bonded in a distorted hexagonal bipyramidal geometry to two Li1+ and six O2- atoms. There are a spread of Mn–O bond distances ranging from 1.99–2.47 Å. In the fifth Mn+3.50+ site, Mn+3.50+ is bonded in a 2-coordinate geometry to two O2- atoms. There is one shorter (1.82 Å) and one longer (1.97 Å) Mn–O bond length. In the sixth Mn+3.50+ site, Mn+3.50+ is bonded in a distorted linear geometry to three O2- atoms. There are a spread of Mn–O bond distances ranging from 1.78–2.20 Å. In the seventh Mn+3.50+ site, Mn+3.50+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 1.99–2.41 Å. In the eighth Mn+3.50+ site, Mn+3.50+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Mn–O bond distances ranging from 2.00–2.39 Å. In the ninth Mn+3.50+ site, Mn+3.50+ is bonded in a 2-coordinate geometry to two O2- atoms. There are one shorter (2.07 Å) and one longer (2.11 Å) Mn–O bond lengths. In the tenth Mn+3.50+ site, Mn+3.50+ is bonded in a 2-coordinate geometry to four O2- atoms. There are a spread of Mn–O bond distances ranging from 1.89–2.27 Å. In the eleventh Mn+3.50+ site, Mn+3.50+ is bonded in a linear geometry to two O2- atoms. There is one shorter (1.75 Å) and one longer (1.78 Å) Mn–O bond length. In the twelfth Mn+3.50+ site, Mn+3.50+ is bonded in a distorted linear geometry to two O2- atoms. There is one shorter (1.78 Å) and one longer (1.80 Å) Mn–O bond length. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the second O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the third O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the fourth O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the fifth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and one Mn+3.50+ atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the seventh O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to three Mn+3.50+ atoms. In the ninth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the tenth O2- site, O2- is bonded in a distorted single-bond geometry to three Mn+3.50+ atoms. In the eleventh O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the twelfth O2- site, O2- is bonded in a distorted single-bond geometry to three Mn+3.50+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted single-bond geometry to three Mn+3.50+ atoms. In the fourteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the fifteenth O2- site, O2- is bonded in a distorted single-bond geometry to two Mn+3.50+ atoms. In the sixteenth O2- site, O2- is bonded in a distorted single-bond geometry to two Mn+3.50+ atoms. In the seventeenth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the eighteenth O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the nineteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and one Mn+3.50+ atom. In the twentieth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the twenty-first O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the twenty-second O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the twenty-third O2- site, O2- is bonded in a 1-coordinate geometry to one Li1+ and two Mn+3.50+ atoms. In the twenty-fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Li1+ and one Mn+3.50+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on LiMn2O4 by Materials Project

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

36 MATERIALS SCIENCE↗
DOE OSTI2025

Solvent Determines the Formation Pathway in Sol–Gel Synthesized Disordered Rock Salt Material for Lithium Ion Battery Application

The increasing demand for lithium-ion batteries with high capacity and cycling stability, in combination with the scarcity of cobalt and nickel, has led to significant efforts to develop new cathode materials based on earth-abundant transition metals. Mn- and Ti-based disordered rock salt (DRX) cathodes are promising candidates fulfilling these requirements. However, their large-scale fabrication can be energy- and time-intensive using traditional fabrication methods, e.g., solid-state synthesis. The present study showcases sol-gel synthesis as an alternative method with control over the crystallization pathway through solvent choice. Dimethylformamide (DMF) aids the homogenization of the transition metals during early crystallization stages and formation of Li2TiO3 and LiMn2O4 intermediates before the DRX phase is formed. In contrast, 2-methoxyethanol (2-ME) shows transition metal segregation and formation of an additional transition metal intermediate (Ti2MnO4) while not resulting in phase-pure DRX material after calcination. Coin cells prepared with DMF-material yield higher capacity and cycling stability compared with 2-ME material.

Kodalle, Tim↗
DOE OSTI2024

An orbital strategy for regulating the Jahn–Teller effect

ABSTRACT The Jahn–Teller effect (JTE) arising from lattice–electron coupling is a fascinating phenomenon that profoundly affects important physical properties in a number of transition-metal compounds. Controlling JT distortions and their corresponding electronic structures is highly desirable to tailor the functionalities of materials. Here, we propose a local coordinate strategy to regulate the JTE through quantifying occupancy in the ${{d}_{{{z}^2}}}$ and ${{d}_{{{x}^2} - {{y}^2}}}$ orbitals of Mn and scrutinizing the symmetries of the ligand oxygen atoms in MnO6 octahedra in LiMn2O4 and Li0.5Mn2O4. The effectiveness of such a strategy has been demonstrated by constructing P2-type NaLixMn1–xO2 oxides with different Li/Mn ordering schemes. In addition, this strategy is also tenable for most 3d transition-metal compounds in spinel and perovskite frameworks, indicating the universality of local coordinate strategy and the tunability of the lattice–orbital coupling in transition-metal oxides. This work demonstrates a useful strategy to regulate JT distortion and provides useful guidelines for future design of functional materials with specific physical properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Cathode Electrolyte Diagnostics Based on Scanning Probe Microscopy

Various processes lead to degradation of cathodes in lithium-ion batteries. Questions remain regarding mechanisms of many of these processes. Probe microscopy methods including scanning electrochemical microscopy (SECM) are capable of directly probing processes at the cathode/electrolyte interface. SECM uses a small electrode to perform rapid electrochemical analysis of transient species generated at an active cathode/electrolyte interface. This paper discusses the background of the SECM instrument and its application to lithium-ion battery research. We also describe the application of SECM methods to the study of cathode degradation processes observed in lithium-ion batteries. Specifically, we focus on characterizing the dissolution of manganese from LiMn2O4 (LMO) based on recent debate in the literature. We describe experiments to observe and characterize the electrochemical properties of manganese complexes emerging from degrading LMO electrode materials.

cathode/electrolyte interface↗
DOE OSTI2024

Electrolyte and Cutoff Potential Effects on Cycle Life of Li4Ti5O12/LiNi0.9Mn0.1O2 Batteries for Behind-the-Meter Storage Applications

Behind-the-Meter Storage (BTMS) is a stationary battery energy storage system that is connected to the electrical distribution system on the customer's side of the utility's service meter. BTMS systems are used to store electrical energy from the grid as well as inconstant, renewable energy, such as local solar and wind generation. A successful BTMS system will allow the customer to pair their energy generation and storage to optimize electrical consumption from the grid, improving reliability and minimizing cost. For BTMS applications, batteries must be designed and optimized with different set of criteria from other leading segments of the Li-ion battery market, like transportation, due the system being stationary and proximal to the residential or commercial building it's benefitting. BTMS applications prioritize safety, cost (low/no-critical materials), reliability (20-year calendar life), and durability (10,000 cycle life), while having the ability to (minimally) compromise energy density and rate capability. Lithium titanate (Li4Ti5O12-, LTO) is a promising anode candidate for BTMS applications due to its high safety and capacity retention, while maintaining a reasonable 160 mAhg-1 reversable capacity and composition of relatively abundant materials. (1) Specifically, LTO has a high working voltage which helps to prevent Li dendrite formation, improving safety. Furthermore, LTO also has negligible lithiation-based volume change, leading to less mechanical pulverization, or loss of active material, upon cycling. For the cathode, materials with little or no Co are of high interest due to the high cost and low abundance of Co. LiMn2O4 (LMO) has been paired with LTO for BTMS applications in the past due to its safety, low cost (abundancy), and reasonably high operating voltage. (2-4) However, the low capacity of LMO limits energy density and specific energy. While not the highest priority for BTMS applications, increasing energy density will enable deployment in space constrained BTMS applications and decrease total cost. LiNi0.9Mn0.1O2 (LN-MO) is a recently developed material with promise due to its high operating voltage and relatively low price. (5) However, Ni-rich layered oxides, including LNMO, tend to struggle with capacity retention during high-voltage cycling due to mechanical pulverization, irreversible phase transitions, and unstable solid-electrolyte interphase. The study presented here focuses on building an understanding of how electrolyte solvent and varied cutoff potentials will impact the cycle life of LTO/LN-MO cells. Specifically, a comparison is provided between ethylene carbonate (EC), ethyl methyl carbonate (EMC), fluoroethylene carbonate (FEC), and Gen2 electrolyte solvents with 1M Lithium hexafluorophosphate (LiPF6) salt, cycling to two upper termination potentials, 2.6V and 2.7V. Electrochemical testing and diagnostics (e.g., differential capacity analysis, area specific impedance, constant voltage hold, and rate capability) and post-mortem characterization will be used to understand the aging behavior and failure mechanisms of the 8 cell combinations (four electrolytes and two voltage cutoffs). Cells with FEC electrolyte showed a lower initial capacity compared to cells with Gen2, EMC, and EC cycling at both voltages; however, the cells with FEC showed consistent trends in capacity retention with 2.6V and 2.7V termination potentials, while the cells with the other electrolytes showed much higher rates of capacity loss when cycling to the higher voltage. These results indicate that FEC may play a role in improving durability of high-voltage, Ni-rich electrode systems for use in high-cycle applications, such as BTMS.

electrolyte↗