Cation Conductivity of Li8ZrO6–LiYO2Solid Solutions

Pantyukhina, M. I.; Andreev, O. L.; Martem’yanova, Z. S.; Баталов, Н. Н.

doi:10.1023/b:inma.0000023965.10888.eb

Cited by 5 publications

(6 citation statements)

References 3 publications

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“…A low level (0.04) of Mg or Nb doping improves the room-temperature ionic conductivity of LZO by an order of magnitude. A similar trend was observed in some high-temperature measurements . To balance the charge, the introduction of Mg or Nb results in the formation of lithium vacancies, which increases the total number of charge carriers.…”

Section: Resultssupporting

confidence: 84%

“…Li 8 ZrO 6 has a layered structure with two kinds of Li atoms. One kind of lithium atom (labeled as 2, 3, 4,5,6,7,10,11,12,13,14,15,18,19,20,21,22,23) occupies the tetrahedral voids formed by the face-centered-cubic oxygen sublattice, and the other kind (labeled as 1,8,9,16,17,24) occupies the octahedral voids formed by the face-centeredcubic oxygen lattice. All zirconium atoms are equivalent.…”

Section: Resultsmentioning

confidence: 99%

“…A similar trend was observed in some hightemperature measurements. 19 To balance the charge, the introduction of Mg or Nb results in the formation of lithium vacancies, which increases the total number of charge carriers. However, further increasing the Nb doping level to 0.33 gives only a very slight increase in ionic conductivity (although we will see below that there is a significant change in activation energy).…”

Section: Resultsmentioning

confidence: 99%

“…Doping has long been an important strategy to tune the electronic and ionic conductivity of materials, and doping has been investigated for many electrode materials. − To increase the conductivity and specific capacity of Li 8 ZrO 6 , the effect on electrochemical delithiation and relithiation of doping with Mn 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , and Ce 3+ was investigated . The effect on the high-temperature conductivity of doping Li 8 ZrO 6 with Ce, Nb, Mg, Sr, and Y was also studied in previous papers. − However, most lithium-ion batteries operate at room temperature, so it is important to study the properties of doped Li 8 ZrO 6 at room temperature and to develop a better understanding of the lithium-ion diffusion processes in these materials. It is important to understand the location and stability or instability of the dopants in the lattice in order to understand the role of the dopant in conduction …”

Section: Introductionmentioning

confidence: 99%

“…18 The effect on the high-temperature conductivity of doping Li 8 ZrO 6 with Ce, Nb, Mg, Sr, and Y was also studied in previous papers. 19 −23 However, most lithium-ion batteries operate at room temperature, so it is important to study the properties of doped Li 8 ZrO 6 at room temperature and to develop a better understanding of the lithium-ion diffusion processes in these materials. It is important to understand the location and stability or instability of the dopants in the lattice in order to understand the role of the dopant in conduction.…”

Section: Introductionmentioning

confidence: 99%

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Conduction and Surface Effects in Cathode Materials: Li₈ZrO₆ and Doped Li₈ZrO₆

et al. 2016

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Doped Li8ZrO6 (LZO) is a pseudolayered material under consideration for lithium-ion battery cathodes and solid electrolyte coatings. The effects of doping LZO with Ce, Ti, Mg, Nb, and Y on structure, band gaps, conductivity, and activation energy for ion migration are investigated both experimentally and by quantum mechanical calculations. Optical band gaps decrease for all doped materials compared to undoped LZO. While all dopants reduce the electronic conductivity at room temperature slightly, doping with Mg or Nb increases ionic conductivity by an order of magnitude. Introducing a high loading of Nb into LZO decreases the activation energy for Li-ion diffusion in the 22–120 °C range. Calculations on lithium-ion diffusion in LZO show that it occurs by a polaron–vacancy complex mechanism. The energy barrier is lowest for the lithium hopping in a zigzag fashion between tetrahedral voids within adjacent layers. The diffusion barrier is reduced as the number of Li vacancies increases during battery charging. We calculated surface energies for 10 surfaces, and we find that the most stable surface is the (001) surface with the tetrahedral Li layer being exposed. The delithiation energy on the (001) surface was found to be slightly higher than that in the bulk. The Li-ion diffusion barriers from the surface to the bulk were also calculated on the (001) surface, and the diffusion energy barrier across the (001) surface was found to be smaller than the energy barrier along the (001) direction in the bulk, and also lower than the barrier for the lowest-energy path in the bulk (which is a hop between tetrahedral voids in adjacent layers as shown in the related graphic). These characterizations of surface and doping effects will assist future materials design.

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Section: Resultssupporting

confidence: 84%