Related Experiment Video
Updated: Jun 16, 2025
11:25
In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries
Published on: November 10, 2014
15.7K
Expanding the Phase Space for Halide-Based Solid Electrolytes: Li-Mg-Zr-Cl Spinels.
Christopher L Rom1, Philip Yox2, Abby M Cardoza2
1National Renewable Energy Laboratory, Golden, Colorado 80401, United States.
Chemistry of Materials : a Publication of the American Chemical Society
|August 19, 2024
Summary
Researchers developed new chloride-based solid electrolytes using abundant magnesium and zirconium. These materials show potential for low-cost, all-solid-state lithium batteries, though conductivity needs further optimization.
Area of Science:
- Materials Science
- Electrochemistry
- Solid-state batteries
Background:
- Chloride-based solid electrolytes offer high ionic conductivity and compatibility with high-voltage cathodes for all-solid-state lithium batteries.
- Current leading materials rely on expensive and scarce trivalent metals like scandium, yttrium, and indium.
Purpose of the Study:
- To explore alternative, earth-abundant elements for chloride solid electrolytes.
- To synthesize and characterize novel chloride solid electrolytes using mixed di- and tetra-valent metals.
- To investigate the impact of aliovalent substitution on ionic conductivity.
Main Methods:
- Synthesis of Li2Mg1/3Zr1/3Cl4 with a spinel crystal structure.
- Comparison of ionic conductivity with Li2Sc2/3Cl4.
- Aliovalent substitution studies across the Li2-xMg1-x/3Zrx/3Cl4 series.
Main Results:
- Li2Mg1/3Zr1/3Cl4 exhibits lower ionic conductivity (0.028 mS/cm at 30 °C) compared to Li2Sc2/3Cl4 (1.6 mS/cm at 30 °C).
- Disordered Mg2+ and Zr4+ arrangement in Li2Mg1/3Zr1/3Cl4 is proposed to hinder Li+ ion migration.
- Aliovalent substitution, increasing Zr4+ content, enhances ionic conductivity by introducing Li+ vacancies.
Conclusions:
- The use of mixed di- and tetra-valent metals offers a new avenue for developing chloride-based solid electrolytes.
- Further optimization through aliovalent substitution is crucial for improving ionic conductivity.
- This research paves the way for cost-effective solid-state batteries.
Related Concept Videos
02:42Ionic Crystal Structures
14.2K
Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
14.2K
02:42Valence Bond Theory
8.5K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.5K
02:54Trends in Lattice Energy: Ion Size and Charge
23.8K
An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:
23.8K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
41.8K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
41.8K
02:58Crystal Field Theory - Octahedral Complexes
26.3K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
26.3K
03:02Colors and Magnetism
11.6K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
11.6K