Toward Understanding the Lithium Transport Mechanism in Garnet-type Solid Electrolytes: Li+ Ion Exchanges and Their Mobility at Octahedral/Tetrahedral Sites

Dawei Wang; Guiming Zhong; Wei Kong Pang; Zaiping Guo; Yixiao Li; Matthew J. McDonald; Riqiang Fu; Jin-Xiao Mi; Yong Yang

doi:10.1021/acs.chemmater.5b02429

Toward Understanding the Lithium Transport Mechanism in Garnet-type Solid Electrolytes: Li⁺ Ion Exchanges and Their Mobility at Octahedral/Tetrahedral Sites

Dawei Wang, Guiming Zhong, Wei Kong Pang, Zaiping Guo, Yixiao Li, Matthew J. McDonald, Riqiang Fu^*, Jin-Xiao Mi, Yong Yang

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

136 Citations (Scopus)

Abstract

The cubic garnet-type solid electrolyte Li₇La₃Zr₂O₁₂ with aliovalent doping exhibits a high ionic conductivity, reaching up to ∼10^-3 S/cm at room temperature. Fully understanding the Li⁺ transport mechanism including Li⁺ mobility at different sites is a key topic in this field, and Li_7-2x-3yAl_yLa₃Zr_2-xW_xO₁₂ (0 ≤ x ≤ 1) are selected as target electrolytes. X-ray and neutron diffraction as well as ac impedance results show that a low amount of aliovalent substitution of Zr with W does not obviously affect the crystal structure and the activation energy of Li⁺ ion jumping, but it does noticeably vary the distribution of Li⁺ ions, electrostatic attraction/repulsion, and crystal defects, which increase the lithium jump rate and the creation energy of mobile Li⁺ ions. For the first time, high-resolution NMR results show evidence that the 24d, 96h, and 48g sites can be well-resolved. In addition, ionic exchange between the 24d and 96h sites is clearly observed, demonstrating a lithium transport route of 24d-96h-48g-96h-24d. The lithium mobility at the 24d sites is found to dominate the total ionic conductivity of the samples, with diffusion coefficients of 10^-9 m² s^-1 and 10^-12 m² s^-1 at the octahedral and tetrahedral sites, respectively. © 2015 American Chemical Society.

Original language	English
Pages (from-to)	6650-6659
Journal	Chemistry of Materials
Volume	27
Issue number	19
DOIs	https://doi.org/10.1021/acs.chemmater.5b02429
Publication status	Published - 18 Sept 2015
Externally published	Yes

Bibliographical note

Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to <a href="mailto:[email protected]">[email protected]</a>.

Funding

The National Basic Research Program of China (973 program, Grant no. 2011CB935903) and the National Natural Science Foundation of China (Grant nos. 21233004 and 21021002, and in part 21428303).

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access Output

10.1021/acs.chemmater.5b02429

Other Access Options

Check CityUHK Library

Permanent Link

Right click to copy link

Cite this

@article{2808c22d131b4ec89df24555f80108f7,

title = "Toward Understanding the Lithium Transport Mechanism in Garnet-type Solid Electrolytes: Li+ Ion Exchanges and Their Mobility at Octahedral/Tetrahedral Sites",

abstract = "The cubic garnet-type solid electrolyte Li7La3Zr2O12 with aliovalent doping exhibits a high ionic conductivity, reaching up to ∼10-3 S/cm at room temperature. Fully understanding the Li+ transport mechanism including Li+ mobility at different sites is a key topic in this field, and Li7-2x-3yAlyLa3Zr2-xWxO12 (0 ≤ x ≤ 1) are selected as target electrolytes. X-ray and neutron diffraction as well as ac impedance results show that a low amount of aliovalent substitution of Zr with W does not obviously affect the crystal structure and the activation energy of Li+ ion jumping, but it does noticeably vary the distribution of Li+ ions, electrostatic attraction/repulsion, and crystal defects, which increase the lithium jump rate and the creation energy of mobile Li+ ions. For the first time, high-resolution NMR results show evidence that the 24d, 96h, and 48g sites can be well-resolved. In addition, ionic exchange between the 24d and 96h sites is clearly observed, demonstrating a lithium transport route of 24d-96h-48g-96h-24d. The lithium mobility at the 24d sites is found to dominate the total ionic conductivity of the samples, with diffusion coefficients of 10-9 m2 s-1 and 10-12 m2 s-1 at the octahedral and tetrahedral sites, respectively. {\textcopyright} 2015 American Chemical Society.",

author = "Dawei Wang and Guiming Zhong and Pang, {Wei Kong} and Zaiping Guo and Yixiao Li and McDonald, {Matthew J.} and Riqiang Fu and Jin-Xiao Mi and Yong Yang",

note = "Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to <a href={"}mailto:[email protected]{"}>[email protected]</a>.",

year = "2015",

month = sep,

day = "18",

doi = "10.1021/acs.chemmater.5b02429",

language = "English",

volume = "27",

pages = "6650--6659",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "19",

}

Toward Understanding the Lithium Transport Mechanism in Garnet-type Solid Electrolytes: Li⁺ Ion Exchanges and Their Mobility at Octahedral/Tetrahedral Sites. / Wang, Dawei; Zhong, Guiming; Pang, Wei Kong et al.
In: Chemistry of Materials, Vol. 27, No. 19, 18.09.2015, p. 6650-6659.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Toward Understanding the Lithium Transport Mechanism in Garnet-type Solid Electrolytes

T2 - Li+ Ion Exchanges and Their Mobility at Octahedral/Tetrahedral Sites

AU - Wang, Dawei

AU - Zhong, Guiming

AU - Pang, Wei Kong

AU - Guo, Zaiping

AU - Li, Yixiao

AU - McDonald, Matthew J.

AU - Fu, Riqiang

AU - Mi, Jin-Xiao

AU - Yang, Yong

N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to <a href="mailto:[email protected]">[email protected]</a>.

PY - 2015/9/18

Y1 - 2015/9/18

N2 - The cubic garnet-type solid electrolyte Li7La3Zr2O12 with aliovalent doping exhibits a high ionic conductivity, reaching up to ∼10-3 S/cm at room temperature. Fully understanding the Li+ transport mechanism including Li+ mobility at different sites is a key topic in this field, and Li7-2x-3yAlyLa3Zr2-xWxO12 (0 ≤ x ≤ 1) are selected as target electrolytes. X-ray and neutron diffraction as well as ac impedance results show that a low amount of aliovalent substitution of Zr with W does not obviously affect the crystal structure and the activation energy of Li+ ion jumping, but it does noticeably vary the distribution of Li+ ions, electrostatic attraction/repulsion, and crystal defects, which increase the lithium jump rate and the creation energy of mobile Li+ ions. For the first time, high-resolution NMR results show evidence that the 24d, 96h, and 48g sites can be well-resolved. In addition, ionic exchange between the 24d and 96h sites is clearly observed, demonstrating a lithium transport route of 24d-96h-48g-96h-24d. The lithium mobility at the 24d sites is found to dominate the total ionic conductivity of the samples, with diffusion coefficients of 10-9 m2 s-1 and 10-12 m2 s-1 at the octahedral and tetrahedral sites, respectively. © 2015 American Chemical Society.

AB - The cubic garnet-type solid electrolyte Li7La3Zr2O12 with aliovalent doping exhibits a high ionic conductivity, reaching up to ∼10-3 S/cm at room temperature. Fully understanding the Li+ transport mechanism including Li+ mobility at different sites is a key topic in this field, and Li7-2x-3yAlyLa3Zr2-xWxO12 (0 ≤ x ≤ 1) are selected as target electrolytes. X-ray and neutron diffraction as well as ac impedance results show that a low amount of aliovalent substitution of Zr with W does not obviously affect the crystal structure and the activation energy of Li+ ion jumping, but it does noticeably vary the distribution of Li+ ions, electrostatic attraction/repulsion, and crystal defects, which increase the lithium jump rate and the creation energy of mobile Li+ ions. For the first time, high-resolution NMR results show evidence that the 24d, 96h, and 48g sites can be well-resolved. In addition, ionic exchange between the 24d and 96h sites is clearly observed, demonstrating a lithium transport route of 24d-96h-48g-96h-24d. The lithium mobility at the 24d sites is found to dominate the total ionic conductivity of the samples, with diffusion coefficients of 10-9 m2 s-1 and 10-12 m2 s-1 at the octahedral and tetrahedral sites, respectively. © 2015 American Chemical Society.

UR - http://www.scopus.com/inward/record.url?scp=84944088906&partnerID=8YFLogxK

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-84944088906&origin=recordpage

U2 - 10.1021/acs.chemmater.5b02429

DO - 10.1021/acs.chemmater.5b02429

M3 - RGC 21 - Publication in refereed journal

SN - 0897-4756

VL - 27

SP - 6650

EP - 6659

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 19

ER -