Halogenation of Li7La3Zr2O12 solid electrolytes: a combined solid-state NMR, computational and electrochemical study

Bo Dong; abby haworth; stephen yeandel; Mark Stockham; Matthew James; Jingwei Xiu; damei wang; pooja goddard; karen  johnston; Peter Slater

doi:10.1039/D1TA07309E

Halogenation of Li₇La₃Zr₂O₁₂ solid electrolytes: a combined solid-state NMR, computational and electrochemical study

Bo Dong, abby haworth, stephen yeandel, Mark Stockham, Matthew James, Jingwei Xiu, damei wang, pooja goddard, karen johnston, Peter Slater

Chemistry

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Abstract

Garnet-based solid electrolytes have been proposed as promising candidates for next generation all-solid-state batteries. Whilst multiple cation substitution studies of these garnets have been undertaken to try and improve their overall performance, anion doping of garnets has rarely been attempted, owing to the synthetic challenges associated with this particular doping strategy. In this work, we present the halogenation (F, Cl) of the solid state electrolyte Li₇La₃Zr₂O₁₂ (LLZO) via a low temperature solid state synthetic route using PTFE and PVC polymers. A reduction in tetragonal distortion (F incorporation) and a tetragonal to cubic phase transition (Cl incorporation) is observed in halogenated LLZO, suggesting the replacement of O²⁻ with F⁻ or Cl⁻ is associated with the creation of lithium vacancies. Combined solid-state NMR and computational studies support the presence of F⁻ or Cl⁻ in halogenated LLZO. The effects of surface fluorination were also investigated for Al-doped LLZO (Li_6.4Al_0.2La₃Zr₂O₁₂, LLAZO) with the results suggesting that this strategy has the ability to prevent full dendrite penetration at high current densities (up to 10 mA cm⁻²).

Original language	English
Pages (from-to)	11172-11185
Number of pages	14
Journal	Journal of Materials Chemistry A
Volume	10
Issue number	20
Early online date	4 May 2022
DOIs	https://doi.org/10.1039/D1TA07309E
Publication status	Published - 28 May 2022

Bibliographical note

Funding Information:
PRS and BD acknowledge the support of the EPSRC grant EP/R024006/1: ICSF Wave 1: GENESIS: Garnet Electrolytes for New Energy Storage Integrated Solutions, and EPSRC grant EP/T02349X/1 Capitol Award for Core Equipment. We would like to thank the University of Birmingham for the studentship funding of MPS and MSJ. KEJ and ARH would like to thank Dr David Apperley for experimental assistance and the EPRSC for an EPSRC Doctoral Partnership award (EP/N509462/1). PG and SRY acknowledge the support of EPSRC SUPERGEN grant, EP/N001982/1. PG and SRY are grateful for the use of the ‘Hydra’ High Performance System at Loughborough University in addition to time on the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) supplied via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431). PG and SRY strongly acknowledge the use of Athena as part of the HPC Midlands+ consortium, funded by the EPSRC on grant EP/P020232/1. Raw experimental data can be found at: https://doi.org/10.25500/edata.bham.00000799.

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10.1039/D1TA07309ELicence: Creative Commons: Attribution (CC BY)

DongB2022HalogenationFinal published version, 1.81 MBLicence: Creative Commons: Attribution (CC BY)

https://pubs.rsc.org/en/content/articlelanding/2022/TA/D1TA07309ELicence: Creative Commons: Attribution (CC BY)

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

Research data supporting the publication "Halogenation of Li7La3Zr2O12 Solid Electrolytes: A Combined Solid-State NMR, Computational and Electrochemical Study"
Dong, B. (Creator), Haworth, A. (Creator), Yeandel, S. (Creator), Stockham, M. (Creator), James, M. (Creator), Xiu, J. (Creator), Wang, D. (Creator), goddard, P. (Creator), Johnston, K. (Creator) & Slater, P. (Creator), University of Birmingham, 25 Feb 2022
DOI: https://doi.org/10.25500/edata.bham.00000799
Dataset

Cite this

@article{52cf3256f2574769a44307846ac709ca,

title = "Halogenation of Li7La3Zr2O12 solid electrolytes: a combined solid-state NMR, computational and electrochemical study",

abstract = "Garnet-based solid electrolytes have been proposed as promising candidates for next generation all-solid-state batteries. Whilst multiple cation substitution studies of these garnets have been undertaken to try and improve their overall performance, anion doping of garnets has rarely been attempted, owing to the synthetic challenges associated with this particular doping strategy. In this work, we present the halogenation (F, Cl) of the solid state electrolyte Li7La3Zr2O12 (LLZO) via a low temperature solid state synthetic route using PTFE and PVC polymers. A reduction in tetragonal distortion (F incorporation) and a tetragonal to cubic phase transition (Cl incorporation) is observed in halogenated LLZO, suggesting the replacement of O2− with F− or Cl− is associated with the creation of lithium vacancies. Combined solid-state NMR and computational studies support the presence of F− or Cl− in halogenated LLZO. The effects of surface fluorination were also investigated for Al-doped LLZO (Li6.4Al0.2La3Zr2O12, LLAZO) with the results suggesting that this strategy has the ability to prevent full dendrite penetration at high current densities (up to 10 mA cm−2).",

author = "Bo Dong and abby haworth and stephen yeandel and Mark Stockham and Matthew James and Jingwei Xiu and damei wang and pooja goddard and karen johnston and Peter Slater",

note = "Funding Information: PRS and BD acknowledge the support of the EPSRC grant EP/R024006/1: ICSF Wave 1: GENESIS: Garnet Electrolytes for New Energy Storage Integrated Solutions, and EPSRC grant EP/T02349X/1 Capitol Award for Core Equipment. We would like to thank the University of Birmingham for the studentship funding of MPS and MSJ. KEJ and ARH would like to thank Dr David Apperley for experimental assistance and the EPRSC for an EPSRC Doctoral Partnership award (EP/N509462/1). PG and SRY acknowledge the support of EPSRC SUPERGEN grant, EP/N001982/1. PG and SRY are grateful for the use of the {\textquoteleft}Hydra{\textquoteright} High Performance System at Loughborough University in addition to time on the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) supplied via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431). PG and SRY strongly acknowledge the use of Athena as part of the HPC Midlands+ consortium, funded by the EPSRC on grant EP/P020232/1. Raw experimental data can be found at: https://doi.org/10.25500/edata.bham.00000799.",

year = "2022",

month = may,

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doi = "10.1039/D1TA07309E",

language = "English",

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T1 - Halogenation of Li7La3Zr2O12 solid electrolytes

T2 - a combined solid-state NMR, computational and electrochemical study

AU - Dong, Bo

AU - haworth, abby

AU - yeandel, stephen

AU - Stockham, Mark

AU - James, Matthew

AU - Xiu, Jingwei

AU - wang, damei

AU - goddard, pooja

AU - johnston, karen

AU - Slater, Peter

N1 - Funding Information: PRS and BD acknowledge the support of the EPSRC grant EP/R024006/1: ICSF Wave 1: GENESIS: Garnet Electrolytes for New Energy Storage Integrated Solutions, and EPSRC grant EP/T02349X/1 Capitol Award for Core Equipment. We would like to thank the University of Birmingham for the studentship funding of MPS and MSJ. KEJ and ARH would like to thank Dr David Apperley for experimental assistance and the EPRSC for an EPSRC Doctoral Partnership award (EP/N509462/1). PG and SRY acknowledge the support of EPSRC SUPERGEN grant, EP/N001982/1. PG and SRY are grateful for the use of the ‘Hydra’ High Performance System at Loughborough University in addition to time on the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk) supplied via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431). PG and SRY strongly acknowledge the use of Athena as part of the HPC Midlands+ consortium, funded by the EPSRC on grant EP/P020232/1. Raw experimental data can be found at: https://doi.org/10.25500/edata.bham.00000799.

PY - 2022/5/28

Y1 - 2022/5/28

N2 - Garnet-based solid electrolytes have been proposed as promising candidates for next generation all-solid-state batteries. Whilst multiple cation substitution studies of these garnets have been undertaken to try and improve their overall performance, anion doping of garnets has rarely been attempted, owing to the synthetic challenges associated with this particular doping strategy. In this work, we present the halogenation (F, Cl) of the solid state electrolyte Li7La3Zr2O12 (LLZO) via a low temperature solid state synthetic route using PTFE and PVC polymers. A reduction in tetragonal distortion (F incorporation) and a tetragonal to cubic phase transition (Cl incorporation) is observed in halogenated LLZO, suggesting the replacement of O2− with F− or Cl− is associated with the creation of lithium vacancies. Combined solid-state NMR and computational studies support the presence of F− or Cl− in halogenated LLZO. The effects of surface fluorination were also investigated for Al-doped LLZO (Li6.4Al0.2La3Zr2O12, LLAZO) with the results suggesting that this strategy has the ability to prevent full dendrite penetration at high current densities (up to 10 mA cm−2).

AB - Garnet-based solid electrolytes have been proposed as promising candidates for next generation all-solid-state batteries. Whilst multiple cation substitution studies of these garnets have been undertaken to try and improve their overall performance, anion doping of garnets has rarely been attempted, owing to the synthetic challenges associated with this particular doping strategy. In this work, we present the halogenation (F, Cl) of the solid state electrolyte Li7La3Zr2O12 (LLZO) via a low temperature solid state synthetic route using PTFE and PVC polymers. A reduction in tetragonal distortion (F incorporation) and a tetragonal to cubic phase transition (Cl incorporation) is observed in halogenated LLZO, suggesting the replacement of O2− with F− or Cl− is associated with the creation of lithium vacancies. Combined solid-state NMR and computational studies support the presence of F− or Cl− in halogenated LLZO. The effects of surface fluorination were also investigated for Al-doped LLZO (Li6.4Al0.2La3Zr2O12, LLAZO) with the results suggesting that this strategy has the ability to prevent full dendrite penetration at high current densities (up to 10 mA cm−2).

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U2 - 10.1039/D1TA07309E

DO - 10.1039/D1TA07309E

M3 - Article

SN - 2050-7488

VL - 10

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EP - 11185

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

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ER -

Halogenation of Li7La3Zr2O12 solid electrolytes: a combined solid-state NMR, computational and electrochemical study

Abstract

Bibliographical note

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Projects

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

Datasets

Research data supporting the publication "Halogenation of Li7La3Zr2O12 Solid Electrolytes: A Combined Solid-State NMR, Computational and Electrochemical Study"

Cite this

Halogenation of Li₇La₃Zr₂O₁₂ solid electrolytes: a combined solid-state NMR, computational and electrochemical study