Evaluation of the effect of site substitution of Pr doping in the Lithium garnet system Li5La3Nb2O12

Mark Stockham; Bo Dong; Yulong Ding; Yongliang Li; Peter Slater

doi:10.1039/D0DT01497D

Evaluation of the effect of site substitution of Pr doping in the Lithium garnet system Li₅La₃Nb₂O₁₂

Mark Stockham, Bo Dong, Yulong Ding, Yongliang Li, Peter Slater

Research output: Contribution to journal › Article › peer-review

3 Citations (Scopus)

186 Downloads (Pure)

Abstract

Li ion conducting garnets have been attracting considerable interest for use as the electrolyte in all solidstate batteries, due to their high ionic conductivity and wide electrochemical stability window. Consequently, there have been a number of doping studies aimed at optimising the conductivity, focusing on both doping in Li₇La₃Zr₂O₁₂ and Li₅La₃(Nb/Ta)₂O₁₂ systems. In this paper, we report a detailed study of Pr doping in Li₅La₃Nb₂O₁₂, and show that this is a rare example of an ambi-site dopant, being able to be doped onto either the La or Nb site. Interestingly the resultant Pr oxidation state is determined by the site substitution, with oxidation states of 3+ for the La site, and 4+ for the Nb site. While the conductivity is essentially unchanged for the La site substitution, Pr4+ substitution on the Nb site leads to a large increase in the conductivity associated with the increase in Li content (Li_5+xLa₃Nb_2−xPr_xO₁₂) up to 0.56 mS cm⁻¹(at 50 °C) for x = 0.8. Overall, this work highlights the flexibility of these garnet materials to doping, and suggests that further consideration of site substitution be considered for other dopants.

Original language	English
Pages (from-to)	10349-10359
Number of pages	11
Journal	Dalton Transactions
Volume	49
Issue number	30
Early online date	29 May 2020
DOIs	https://doi.org/10.1039/D0DT01497D
Publication status	Published - 14 Aug 2020

Bibliographical note

Funding Information:
We would like to thank the University of Birmingham for the studentship funding of Mark Stockham and the EPSRC for funding the GENESIS project (under EP/R024006/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We would also like to thank Prof. Emma Kendrick for the continued use of the dry room facilities. Raw experimental data can be found at: https://doi.org/10.25500/edata.bham.00000490.

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10.1039/D0DT01497DLicence: Creative Commons: Attribution-NonCommercial (CC BY-NC)

Stockham_et_al_Evaluation_of_the_effect_of_site_substitution_Dalton_Transactions_2020Final published version, 9.28 MBLicence: Creative Commons: Attribution-NonCommercial (CC BY-NC)

https://pubs.rsc.org/en/content/articlelanding/2020/DT/D0DT01497DLicence: Creative Commons: Attribution-NonCommercial (CC BY-NC)

ICSF Wave 1: GENESIS: Garnet Electrolytes for New Energy Storage Integrated Solutions
Ding, Y. (Co-Investigator), Slater, P. (Principal Investigator) & Li, Y. (Co-Investigator)
Engineering & Physical Science Research Council
1/10/17 → 28/02/21
Project: Research Councils

Research data supporting "Evaluation of the effect of site substitution of Pr doping in the Lithium garnet system Li5La3Nb2O12"
Stockham, M. (Creator), Dong, B. (Creator), Li, Y. (Creator), Ding, Y. (Creator) & Slater, P. (Creator), University of Birmingham, 2020
DOI: 10.25500/edata.bham.00000490
Dataset

Cite this

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title = "Evaluation of the effect of site substitution of Pr doping in the Lithium garnet system Li5La3Nb2O12",

abstract = "Li ion conducting garnets have been attracting considerable interest for use as the electrolyte in all solidstate batteries, due to their high ionic conductivity and wide electrochemical stability window. Consequently, there have been a number of doping studies aimed at optimising the conductivity, focusing on both doping in Li7La3Zr2O12 and Li5La3(Nb/Ta)2O12 systems. In this paper, we report a detailed study of Pr doping in Li5La3Nb2O12, and show that this is a rare example of an ambi-site dopant, being able to be doped onto either the La or Nb site. Interestingly the resultant Pr oxidation state is determined by the site substitution, with oxidation states of 3+ for the La site, and 4+ for the Nb site. While the conductivity is essentially unchanged for the La site substitution, Pr4+ substitution on the Nb site leads to a large increase in the conductivity associated with the increase in Li content (Li5+xLa3Nb2−xPrxO12) up to 0.56 mS cm−1 (at 50 °C) for x = 0.8. Overall, this work highlights the flexibility of these garnet materials to doping, and suggests that further consideration of site substitution be considered for other dopants.",

author = "Mark Stockham and Bo Dong and Yulong Ding and Yongliang Li and Peter Slater",

note = "Funding Information: We would like to thank the University of Birmingham for the studentship funding of Mark Stockham and the EPSRC for funding the GENESIS project (under EP/R024006/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We would also like to thank Prof. Emma Kendrick for the continued use of the dry room facilities. Raw experimental data can be found at: https://doi.org/10.25500/edata.bham.00000490.",

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AU - Slater, Peter

N1 - Funding Information: We would like to thank the University of Birmingham for the studentship funding of Mark Stockham and the EPSRC for funding the GENESIS project (under EP/R024006/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We would also like to thank Prof. Emma Kendrick for the continued use of the dry room facilities. Raw experimental data can be found at: https://doi.org/10.25500/edata.bham.00000490.

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N2 - Li ion conducting garnets have been attracting considerable interest for use as the electrolyte in all solidstate batteries, due to their high ionic conductivity and wide electrochemical stability window. Consequently, there have been a number of doping studies aimed at optimising the conductivity, focusing on both doping in Li7La3Zr2O12 and Li5La3(Nb/Ta)2O12 systems. In this paper, we report a detailed study of Pr doping in Li5La3Nb2O12, and show that this is a rare example of an ambi-site dopant, being able to be doped onto either the La or Nb site. Interestingly the resultant Pr oxidation state is determined by the site substitution, with oxidation states of 3+ for the La site, and 4+ for the Nb site. While the conductivity is essentially unchanged for the La site substitution, Pr4+ substitution on the Nb site leads to a large increase in the conductivity associated with the increase in Li content (Li5+xLa3Nb2−xPrxO12) up to 0.56 mS cm−1 (at 50 °C) for x = 0.8. Overall, this work highlights the flexibility of these garnet materials to doping, and suggests that further consideration of site substitution be considered for other dopants.

AB - Li ion conducting garnets have been attracting considerable interest for use as the electrolyte in all solidstate batteries, due to their high ionic conductivity and wide electrochemical stability window. Consequently, there have been a number of doping studies aimed at optimising the conductivity, focusing on both doping in Li7La3Zr2O12 and Li5La3(Nb/Ta)2O12 systems. In this paper, we report a detailed study of Pr doping in Li5La3Nb2O12, and show that this is a rare example of an ambi-site dopant, being able to be doped onto either the La or Nb site. Interestingly the resultant Pr oxidation state is determined by the site substitution, with oxidation states of 3+ for the La site, and 4+ for the Nb site. While the conductivity is essentially unchanged for the La site substitution, Pr4+ substitution on the Nb site leads to a large increase in the conductivity associated with the increase in Li content (Li5+xLa3Nb2−xPrxO12) up to 0.56 mS cm−1 (at 50 °C) for x = 0.8. Overall, this work highlights the flexibility of these garnet materials to doping, and suggests that further consideration of site substitution be considered for other dopants.

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Evaluation of the effect of site substitution of Pr doping in the Lithium garnet system Li5La3Nb2O12

Abstract

Bibliographical note

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Projects

ICSF Wave 1: GENESIS: Garnet Electrolytes for New Energy Storage Integrated Solutions

Datasets

Research data supporting "Evaluation of the effect of site substitution of Pr doping in the Lithium garnet system Li5La3Nb2O12"

Cite this

Evaluation of the effect of site substitution of Pr doping in the Lithium garnet system Li₅La₃Nb₂O₁₂