---
_id: '14687'
abstract:
- lang: eng
text: The short history of research on Li-O2 batteries has seen a remarkable number
of mechanistic U-turns over the years. From the initial use of carbonate electrolytes,
that were then found to be entirely unsuitable, to the belief that (su)peroxide
was solely responsible for degradation, before the more reactive singlet oxygen
was found to form, to the hypothesis that capacity depends on a competing surface/solution
mechanism before a practically exclusive solution mechanism was identified. Herein,
we argue for an ever-fresh look at the reported data without bias towards supposedly
established explanations. We explain how the latest findings on rate and capacity
limits, as well as the origin of side reactions, are connected via the disproportionation
(DISP) step in the (dis)charge mechanism. Therefrom, directions emerge for the
design of electrolytes and mediators on how to suppress side reactions and to
enable high rate and high reversible capacity.
article_number: e202316476
article_processing_charge: Yes (via OA deal)
article_type: review
author:
- first_name: Rajesh B
full_name: Jethwa, Rajesh B
id: 4cc538d5-803f-11ed-ab7e-8139573aad8f
last_name: Jethwa
orcid: 0000-0002-0404-4356
- first_name: Soumyadip
full_name: Mondal, Soumyadip
id: d25d21ef-dc8d-11ea-abe3-ec4576307f48
last_name: Mondal
- first_name: Bhargavi
full_name: Pant, Bhargavi
id: 50c64d4d-eb97-11eb-a6c2-d33e5e14f112
last_name: Pant
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
citation:
ama: Jethwa RB, Mondal S, Pant B, Freunberger SA. To DISP or not? The far‐reaching
reaction mechanisms underpinning Lithium‐air batteries. Angewandte Chemie International
Edition. 2023. doi:10.1002/anie.202316476
apa: Jethwa, R. B., Mondal, S., Pant, B., & Freunberger, S. A. (2023). To DISP
or not? The far‐reaching reaction mechanisms underpinning Lithium‐air batteries.
Angewandte Chemie International Edition. Wiley. https://doi.org/10.1002/anie.202316476
chicago: Jethwa, Rajesh B, Soumyadip Mondal, Bhargavi Pant, and Stefan Alexander
Freunberger. “To DISP or Not? The Far‐reaching Reaction Mechanisms Underpinning
Lithium‐air Batteries.” Angewandte Chemie International Edition. Wiley,
2023. https://doi.org/10.1002/anie.202316476.
ieee: R. B. Jethwa, S. Mondal, B. Pant, and S. A. Freunberger, “To DISP or not?
The far‐reaching reaction mechanisms underpinning Lithium‐air batteries,” Angewandte
Chemie International Edition. Wiley, 2023.
ista: Jethwa RB, Mondal S, Pant B, Freunberger SA. 2023. To DISP or not? The far‐reaching
reaction mechanisms underpinning Lithium‐air batteries. Angewandte Chemie International
Edition., e202316476.
mla: Jethwa, Rajesh B., et al. “To DISP or Not? The Far‐reaching Reaction Mechanisms
Underpinning Lithium‐air Batteries.” Angewandte Chemie International Edition,
e202316476, Wiley, 2023, doi:10.1002/anie.202316476.
short: R.B. Jethwa, S. Mondal, B. Pant, S.A. Freunberger, Angewandte Chemie International
Edition (2023).
date_created: 2023-12-15T16:10:13Z
date_published: 2023-12-14T00:00:00Z
date_updated: 2024-02-15T14:43:05Z
day: '14'
department:
- _id: StFr
- _id: GradSch
doi: 10.1002/anie.202316476
keyword:
- General Chemistry
- Catalysis
language:
- iso: eng
main_file_link:
- open_access: '1'
url: ' https://doi.org/10.1002/anie.202316476'
month: '12'
oa: 1
oa_version: Published Version
publication: Angewandte Chemie International Edition
publication_identifier:
eissn:
- 1521-3773
issn:
- 1433-7851
publication_status: epub_ahead
publisher: Wiley
quality_controlled: '1'
scopus_import: '1'
status: public
title: To DISP or not? The far‐reaching reaction mechanisms underpinning Lithium‐air
batteries
type: journal_article
user_id: 3E5EF7F0-F248-11E8-B48F-1D18A9856A87
year: '2023'
...
---
_id: '14701'
article_processing_charge: No
article_type: review
author:
- first_name: Lynden A.
full_name: Archer, Lynden A.
last_name: Archer
- first_name: Peter G.
full_name: Bruce, Peter G.
last_name: Bruce
- first_name: Ernesto J.
full_name: Calvo, Ernesto J.
last_name: Calvo
- first_name: Daniel
full_name: Dewar, Daniel
last_name: Dewar
- first_name: James H. J.
full_name: Ellison, James H. J.
last_name: Ellison
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Xiangwen
full_name: Gao, Xiangwen
last_name: Gao
- first_name: Laurence J.
full_name: Hardwick, Laurence J.
last_name: Hardwick
- first_name: Gabriela
full_name: Horwitz, Gabriela
last_name: Horwitz
- first_name: Jürgen
full_name: Janek, Jürgen
last_name: Janek
- first_name: Lee R.
full_name: Johnson, Lee R.
last_name: Johnson
- first_name: Jack W.
full_name: Jordan, Jack W.
last_name: Jordan
- first_name: Shoichi
full_name: Matsuda, Shoichi
last_name: Matsuda
- first_name: Svetlana
full_name: Menkin, Svetlana
last_name: Menkin
- first_name: Soumyadip
full_name: Mondal, Soumyadip
id: d25d21ef-dc8d-11ea-abe3-ec4576307f48
last_name: Mondal
- first_name: Qianyuan
full_name: Qiu, Qianyuan
last_name: Qiu
- first_name: Thukshan
full_name: Samarakoon, Thukshan
last_name: Samarakoon
- first_name: Israel
full_name: Temprano, Israel
last_name: Temprano
- first_name: Kohei
full_name: Uosaki, Kohei
last_name: Uosaki
- first_name: Ganesh
full_name: Vailaya, Ganesh
last_name: Vailaya
- first_name: Eric D.
full_name: Wachsman, Eric D.
last_name: Wachsman
- first_name: Yiying
full_name: Wu, Yiying
last_name: Wu
- first_name: Shen
full_name: Ye, Shen
last_name: Ye
citation:
ama: 'Archer LA, Bruce PG, Calvo EJ, et al. Towards practical metal–oxygen batteries:
General discussion. Faraday Discussions. 2023. doi:10.1039/d3fd90062b'
apa: 'Archer, L. A., Bruce, P. G., Calvo, E. J., Dewar, D., Ellison, J. H. J., Freunberger,
S. A., … Ye, S. (2023). Towards practical metal–oxygen batteries: General discussion.
Faraday Discussions. Royal Society of Chemistry. https://doi.org/10.1039/d3fd90062b'
chicago: 'Archer, Lynden A., Peter G. Bruce, Ernesto J. Calvo, Daniel Dewar, James
H. J. Ellison, Stefan Alexander Freunberger, Xiangwen Gao, et al. “Towards Practical
Metal–Oxygen Batteries: General Discussion.” Faraday Discussions. Royal
Society of Chemistry, 2023. https://doi.org/10.1039/d3fd90062b.'
ieee: 'L. A. Archer et al., “Towards practical metal–oxygen batteries: General
discussion,” Faraday Discussions. Royal Society of Chemistry, 2023.'
ista: 'Archer LA, Bruce PG, Calvo EJ, Dewar D, Ellison JHJ, Freunberger SA, Gao
X, Hardwick LJ, Horwitz G, Janek J, Johnson LR, Jordan JW, Matsuda S, Menkin S,
Mondal S, Qiu Q, Samarakoon T, Temprano I, Uosaki K, Vailaya G, Wachsman ED, Wu
Y, Ye S. 2023. Towards practical metal–oxygen batteries: General discussion. Faraday
Discussions.'
mla: 'Archer, Lynden A., et al. “Towards Practical Metal–Oxygen Batteries: General
Discussion.” Faraday Discussions, Royal Society of Chemistry, 2023, doi:10.1039/d3fd90062b.'
short: L.A. Archer, P.G. Bruce, E.J. Calvo, D. Dewar, J.H.J. Ellison, S.A. Freunberger,
X. Gao, L.J. Hardwick, G. Horwitz, J. Janek, L.R. Johnson, J.W. Jordan, S. Matsuda,
S. Menkin, S. Mondal, Q. Qiu, T. Samarakoon, I. Temprano, K. Uosaki, G. Vailaya,
E.D. Wachsman, Y. Wu, S. Ye, Faraday Discussions (2023).
date_created: 2023-12-20T10:48:09Z
date_published: 2023-12-19T00:00:00Z
date_updated: 2023-12-20T11:54:06Z
day: '19'
department:
- _id: StFr
doi: 10.1039/d3fd90062b
keyword:
- Physical and Theoretical Chemistry
language:
- iso: eng
month: '12'
oa_version: None
publication: Faraday Discussions
publication_identifier:
eissn:
- 1364-5498
issn:
- 1359-6640
publication_status: epub_ahead
publisher: Royal Society of Chemistry
quality_controlled: '1'
status: public
title: 'Towards practical metal–oxygen batteries: General discussion'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
year: '2023'
...
---
_id: '14702'
article_processing_charge: No
article_type: review
author:
- first_name: Gary A.
full_name: Attard, Gary A.
last_name: Attard
- first_name: Ernesto J.
full_name: Calvo, Ernesto J.
last_name: Calvo
- first_name: Larry A.
full_name: Curtiss, Larry A.
last_name: Curtiss
- first_name: Daniel
full_name: Dewar, Daniel
last_name: Dewar
- first_name: James H. J.
full_name: Ellison, James H. J.
last_name: Ellison
- first_name: Xiangwen
full_name: Gao, Xiangwen
last_name: Gao
- first_name: Clare P.
full_name: Grey, Clare P.
last_name: Grey
- first_name: Laurence J.
full_name: Hardwick, Laurence J.
last_name: Hardwick
- first_name: Gabriela
full_name: Horwitz, Gabriela
last_name: Horwitz
- first_name: Juergen
full_name: Janek, Juergen
last_name: Janek
- first_name: Lee R.
full_name: Johnson, Lee R.
last_name: Johnson
- first_name: Jack W.
full_name: Jordan, Jack W.
last_name: Jordan
- first_name: Shoichi
full_name: Matsuda, Shoichi
last_name: Matsuda
- first_name: Soumyadip
full_name: Mondal, Soumyadip
id: d25d21ef-dc8d-11ea-abe3-ec4576307f48
last_name: Mondal
- first_name: Alex R.
full_name: Neale, Alex R.
last_name: Neale
- first_name: Nagore
full_name: Ortiz-Vitoriano, Nagore
last_name: Ortiz-Vitoriano
- first_name: Israel
full_name: Temprano, Israel
last_name: Temprano
- first_name: Ganesh
full_name: Vailaya, Ganesh
last_name: Vailaya
- first_name: Eric D.
full_name: Wachsman, Eric D.
last_name: Wachsman
- first_name: Hsien-Hau
full_name: Wang, Hsien-Hau
last_name: Wang
- first_name: Yiying
full_name: Wu, Yiying
last_name: Wu
- first_name: Shen
full_name: Ye, Shen
last_name: Ye
citation:
ama: 'Attard GA, Calvo EJ, Curtiss LA, et al. Materials for stable metal–oxygen
battery cathodes: general discussion. Faraday Discussions. 2023. doi:10.1039/d3fd90059b'
apa: 'Attard, G. A., Calvo, E. J., Curtiss, L. A., Dewar, D., Ellison, J. H. J.,
Gao, X., … Ye, S. (2023). Materials for stable metal–oxygen battery cathodes:
general discussion. Faraday Discussions. Royal Society of Chemistry. https://doi.org/10.1039/d3fd90059b'
chicago: 'Attard, Gary A., Ernesto J. Calvo, Larry A. Curtiss, Daniel Dewar, James
H. J. Ellison, Xiangwen Gao, Clare P. Grey, et al. “Materials for Stable Metal–Oxygen
Battery Cathodes: General Discussion.” Faraday Discussions. Royal Society
of Chemistry, 2023. https://doi.org/10.1039/d3fd90059b.'
ieee: 'G. A. Attard et al., “Materials for stable metal–oxygen battery cathodes:
general discussion,” Faraday Discussions. Royal Society of Chemistry, 2023.'
ista: 'Attard GA, Calvo EJ, Curtiss LA, Dewar D, Ellison JHJ, Gao X, Grey CP, Hardwick
LJ, Horwitz G, Janek J, Johnson LR, Jordan JW, Matsuda S, Mondal S, Neale AR,
Ortiz-Vitoriano N, Temprano I, Vailaya G, Wachsman ED, Wang H-H, Wu Y, Ye S. 2023.
Materials for stable metal–oxygen battery cathodes: general discussion. Faraday
Discussions.'
mla: 'Attard, Gary A., et al. “Materials for Stable Metal–Oxygen Battery Cathodes:
General Discussion.” Faraday Discussions, Royal Society of Chemistry, 2023,
doi:10.1039/d3fd90059b.'
short: G.A. Attard, E.J. Calvo, L.A. Curtiss, D. Dewar, J.H.J. Ellison, X. Gao,
C.P. Grey, L.J. Hardwick, G. Horwitz, J. Janek, L.R. Johnson, J.W. Jordan, S.
Matsuda, S. Mondal, A.R. Neale, N. Ortiz-Vitoriano, I. Temprano, G. Vailaya, E.D.
Wachsman, H.-H. Wang, Y. Wu, S. Ye, Faraday Discussions (2023).
date_created: 2023-12-20T10:49:43Z
date_published: 2023-12-18T00:00:00Z
date_updated: 2023-12-20T11:58:12Z
day: '18'
department:
- _id: StFr
doi: 10.1039/d3fd90059b
keyword:
- Physical and Theoretical Chemistry
language:
- iso: eng
month: '12'
oa_version: None
publication: Faraday Discussions
publication_identifier:
eissn:
- 1364-5498
issn:
- 1359-6640
publication_status: epub_ahead
publisher: Royal Society of Chemistry
quality_controlled: '1'
status: public
title: 'Materials for stable metal–oxygen battery cathodes: general discussion'
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
year: '2023'
...
---
_id: '14733'
abstract:
- lang: eng
text: Redox flow batteries (RFBs) rely on the development of cheap, highly soluble,
and high-energy-density electrolytes. Several candidate quinones have already
been investigated in the literature as two-electron anolytes or catholytes, benefiting
from fast kinetics, high tunability, and low cost. Here, an investigation of nitrogen-rich
fused heteroaromatic quinones was carried out to explore avenues for electrolyte
development. These quinones were synthesized and screened by using electrochemical
techniques. The most promising candidate, 4,8-dioxo-4,8-dihydrobenzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-1,5-diide
(−0.68 V(SHE)), was tested in both an asymmetric and symmetric full-cell setup
resulting in capacity fade rates of 0.35% per cycle and 0.0124% per cycle, respectively.
In situ ultraviolet-visible spectroscopy (UV–Vis), nuclear magnetic resonance
(NMR), and electron paramagnetic resonance (EPR) spectroscopies were used to investigate
the electrochemical stability of the charged species during operation. UV–Vis
spectroscopy, supported by density functional theory (DFT) modeling, reaffirmed
that the two-step charging mechanism observed during battery operation consisted
of two, single-electron transfers. The radical concentration during battery operation
and the degree of delocalization of the unpaired electron were quantified with
NMR and EPR spectroscopy.
article_processing_charge: Yes (in subscription journal)
article_type: original
author:
- first_name: Rajesh B
full_name: Jethwa, Rajesh B
id: 4cc538d5-803f-11ed-ab7e-8139573aad8f
last_name: Jethwa
orcid: 0000-0002-0404-4356
- first_name: Dominic
full_name: Hey, Dominic
last_name: Hey
- first_name: Rachel N.
full_name: Kerber, Rachel N.
last_name: Kerber
- first_name: Andrew D.
full_name: Bond, Andrew D.
last_name: Bond
- first_name: Dominic S.
full_name: Wright, Dominic S.
last_name: Wright
- first_name: Clare P.
full_name: Grey, Clare P.
last_name: Grey
citation:
ama: Jethwa RB, Hey D, Kerber RN, Bond AD, Wright DS, Grey CP. Exploring the landscape
of heterocyclic quinones for redox flow batteries. ACS Applied Energy Materials.
2023. doi:10.1021/acsaem.3c02223
apa: Jethwa, R. B., Hey, D., Kerber, R. N., Bond, A. D., Wright, D. S., & Grey,
C. P. (2023). Exploring the landscape of heterocyclic quinones for redox flow
batteries. ACS Applied Energy Materials. American Chemical Society. https://doi.org/10.1021/acsaem.3c02223
chicago: Jethwa, Rajesh B, Dominic Hey, Rachel N. Kerber, Andrew D. Bond, Dominic
S. Wright, and Clare P. Grey. “Exploring the Landscape of Heterocyclic Quinones
for Redox Flow Batteries.” ACS Applied Energy Materials. American Chemical
Society, 2023. https://doi.org/10.1021/acsaem.3c02223.
ieee: R. B. Jethwa, D. Hey, R. N. Kerber, A. D. Bond, D. S. Wright, and C. P. Grey,
“Exploring the landscape of heterocyclic quinones for redox flow batteries,” ACS
Applied Energy Materials. American Chemical Society, 2023.
ista: Jethwa RB, Hey D, Kerber RN, Bond AD, Wright DS, Grey CP. 2023. Exploring
the landscape of heterocyclic quinones for redox flow batteries. ACS Applied Energy
Materials.
mla: Jethwa, Rajesh B., et al. “Exploring the Landscape of Heterocyclic Quinones
for Redox Flow Batteries.” ACS Applied Energy Materials, American Chemical
Society, 2023, doi:10.1021/acsaem.3c02223.
short: R.B. Jethwa, D. Hey, R.N. Kerber, A.D. Bond, D.S. Wright, C.P. Grey, ACS
Applied Energy Materials (2023).
date_created: 2024-01-05T09:20:48Z
date_published: 2023-12-28T00:00:00Z
date_updated: 2024-01-08T09:03:01Z
day: '28'
ddc:
- '540'
department:
- _id: StFr
doi: 10.1021/acsaem.3c02223
ec_funded: 1
has_accepted_license: '1'
keyword:
- Electrical and Electronic Engineering
- Materials Chemistry
- Electrochemistry
- Energy Engineering and Power Technology
- Chemical Engineering (miscellaneous)
language:
- iso: eng
license: https://creativecommons.org/licenses/by/4.0/
main_file_link:
- open_access: '1'
url: https://doi.org/10.1021/acsaem.3c02223
month: '12'
oa: 1
oa_version: Published Version
project:
- _id: fc2ed2f7-9c52-11eb-aca3-c01059dda49c
call_identifier: H2020
grant_number: '101034413'
name: 'IST-BRIDGE: International postdoctoral program'
publication: ACS Applied Energy Materials
publication_identifier:
eissn:
- 2574-0962
publication_status: epub_ahead
publisher: American Chemical Society
quality_controlled: '1'
status: public
title: Exploring the landscape of heterocyclic quinones for redox flow batteries
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
year: '2023'
...
---
_id: '12737'
abstract:
- lang: eng
text: The substitution of heavier, more metallic atoms into classical organic ligand
frameworks provides an important strategy for tuning ligand properties, such as
ligand bite and donor character, and is the basis for the emerging area of main-group
supramolecular chemistry. In this paper, we explore two new ligands [E(2-Me-8-qy)3]
[E = Sb (1), Bi (2); qy = quinolyl], allowing a fundamental comparison of their
coordination behavior with classical tris(2-pyridyl) ligands of the type [E′(2-py)3]
(E = a range of bridgehead atoms and groups, py = pyridyl). A range of new coordination
modes to Cu+, Ag+, and Au+ is seen for 1 and 2, in the absence of steric constraints
at the bridgehead and with their more remote N-donor atoms. A particular feature
is the adaptive nature of these new ligands, with the ability to adjust coordination
mode in response to the hard–soft character of coordinated metal ions, influenced
also by the character of the bridgehead atom (Sb or Bi). These features can be
seen in a comparison between [Cu2{Sb(2-Me-8-qy)3}2](PF6)2 (1·CuPF6) and [Cu{Bi(2-Me-8-qy)3}](PF6)
(2·CuPF6), the first containing a dimeric cation in which 1 adopts an unprecedented
intramolecular N,N,Sb-coordination mode while in the second, 2 adopts an unusual
N,N,(π-)C coordination mode. In contrast, the previously reported analogous ligands
[E(6-Me-2-py)3] (E = Sb, Bi; 2-py = 2-pyridyl) show a tris-chelating mode in their
complexes with CuPF6, which is typical for the extensive tris(2-pyridyl) family
with a range of metals. The greater polarity of the Bi–C bond in 2 results in
ligand transfer reactions with Au(I). Although this reactivity is not in itself
unusual, the characterization of several products by single-crystal X-ray diffraction
provides snapshots of the ligand transfer reaction involved, with one of the products
(the bimetallic complex [(BiCl){ClAu2(2-Me-8-qy)3}] (8)) containing a Au2Bi core
in which the shortest Au → Bi donor–acceptor bond to date is observed.
acknowledgement: The authors thank the Walters-Kundert Studentship of Selwyn College
(scholarship for J.E.W.), the Leverhulme Trust (R.G.-R. and D.S.W., grant RPG-2017-146),
the Australian Research Council (A.L.C., DE200100450), the Spanish Ministry of Science
and Innovation (MCI) and the Spanish Ministry of Science, Innovation and Universities
(MCIU) (R.G.-R., PID2021-124691NB-I00, funded by MCIN/AEI/10.13039/501100011033/FEDER,
UE and PGC2018-096880-A-I00, MCIU/AEI/FEDER), The University of Valladolid and Santander
Bank (Fellowship for A.G.-R.), and the U.K. EPSRC and The Royal Dutch Shell plc.
(I-Case award for R.B.J., EP/R511870/1) for financial support. Calculations were
carried out on an in-house Odyssey HPC cluster (Cambridge), and the authors are
grateful for the calculation time used.
article_processing_charge: No
article_type: original
author:
- first_name: Álvaro
full_name: García-Romero, Álvaro
last_name: García-Romero
- first_name: Jessica E.
full_name: Waters, Jessica E.
last_name: Waters
- first_name: Rajesh B
full_name: Jethwa, Rajesh B
id: 4cc538d5-803f-11ed-ab7e-8139573aad8f
last_name: Jethwa
orcid: 0000-0002-0404-4356
- first_name: Andrew D.
full_name: Bond, Andrew D.
last_name: Bond
- first_name: Annie L.
full_name: Colebatch, Annie L.
last_name: Colebatch
- first_name: Raúl
full_name: García-Rodríguez, Raúl
last_name: García-Rodríguez
- first_name: Dominic S.
full_name: Wright, Dominic S.
last_name: Wright
citation:
ama: García-Romero Á, Waters JE, Jethwa RB, et al. Highly adaptive nature of group
15 tris(quinolyl) ligands─studies with coinage metals. Inorganic Chemistry.
2023;62(11):4625-4636. doi:10.1021/acs.inorgchem.3c00057
apa: García-Romero, Á., Waters, J. E., Jethwa, R. B., Bond, A. D., Colebatch, A.
L., García-Rodríguez, R., & Wright, D. S. (2023). Highly adaptive nature of
group 15 tris(quinolyl) ligands─studies with coinage metals. Inorganic Chemistry.
American Chemical Society. https://doi.org/10.1021/acs.inorgchem.3c00057
chicago: García-Romero, Álvaro, Jessica E. Waters, Rajesh B Jethwa, Andrew D. Bond,
Annie L. Colebatch, Raúl García-Rodríguez, and Dominic S. Wright. “Highly Adaptive
Nature of Group 15 Tris(Quinolyl) Ligands─studies with Coinage Metals.” Inorganic
Chemistry. American Chemical Society, 2023. https://doi.org/10.1021/acs.inorgchem.3c00057.
ieee: Á. García-Romero et al., “Highly adaptive nature of group 15 tris(quinolyl)
ligands─studies with coinage metals,” Inorganic Chemistry, vol. 62, no.
11. American Chemical Society, pp. 4625–4636, 2023.
ista: García-Romero Á, Waters JE, Jethwa RB, Bond AD, Colebatch AL, García-Rodríguez
R, Wright DS. 2023. Highly adaptive nature of group 15 tris(quinolyl) ligands─studies
with coinage metals. Inorganic Chemistry. 62(11), 4625–4636.
mla: García-Romero, Álvaro, et al. “Highly Adaptive Nature of Group 15 Tris(Quinolyl)
Ligands─studies with Coinage Metals.” Inorganic Chemistry, vol. 62, no.
11, American Chemical Society, 2023, pp. 4625–36, doi:10.1021/acs.inorgchem.3c00057.
short: Á. García-Romero, J.E. Waters, R.B. Jethwa, A.D. Bond, A.L. Colebatch, R.
García-Rodríguez, D.S. Wright, Inorganic Chemistry 62 (2023) 4625–4636.
date_created: 2023-03-19T23:00:59Z
date_published: 2023-03-08T00:00:00Z
date_updated: 2023-08-01T13:42:59Z
day: '08'
department:
- _id: StFr
doi: 10.1021/acs.inorgchem.3c00057
external_id:
isi:
- '000956110300001'
pmid:
- '36883367'
intvolume: ' 62'
isi: 1
issue: '11'
language:
- iso: eng
month: '03'
oa_version: None
page: 4625-4636
pmid: 1
publication: Inorganic Chemistry
publication_identifier:
eissn:
- 1520-510X
issn:
- 0020-1669
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Highly adaptive nature of group 15 tris(quinolyl) ligands─studies with coinage
metals
type: journal_article
user_id: 4359f0d1-fa6c-11eb-b949-802e58b17ae8
volume: 62
year: '2023'
...
---
_id: '13041'
abstract:
- lang: eng
text: A series of triarylamines was synthesised and screened for their suitability
as catholytes in redox flow batteries using cyclic voltammetry (CV). Tris(4-aminophenyl)amine
was found to be the strongest candidate. Solubility and initial electrochemical
performance were promising; however, polymerisation was observed during electrochemical
cycling leading to rapid capacity fade prescribed to a loss of accessible active
material and the limitation of ion transport processes within the cell. A mixed
electrolyte system of H3PO4 and HCl was found to inhibit polymerisation producing
oligomers that consumed less active material reducing rates of degradation in
the redox flow battery. Under these conditions Coulombic efficiency improved by
over 4 %, the maximum number of cycles more than quadrupled and an additional
theoretical capacity of 20 % was accessed. This paper is, to our knowledge, the
first example of triarylamines as catholytes in all-aqueous redox flow batteries
and emphasises the impact supporting electrolytes can have on electrochemical
performance.
acknowledgement: The authors (N.L.F and R.B.J) would like to acknowledge the funding
contributions of Shell and the EPRSC via I–Case studentships (grants no. EP/V519662/1
and EP/R511870/1 respectively). T.I would like to thank the ERC advanced Investigator
Grant for CPG (EC H2020 835073). Thank you to Zhen Wang from the University of Cambridge
for measuring GPC, the Yusuf Hamied Department of Chemistry's mass spectrometry
service for MS measurements and analysis and Dr Andrew Bond from the University
of Cambridge for XRD measurement and analysis.
article_number: e202300128
article_processing_charge: Yes (in subscription journal)
article_type: original
author:
- first_name: Nadia L.
full_name: Farag, Nadia L.
last_name: Farag
- first_name: Rajesh B
full_name: Jethwa, Rajesh B
id: 4cc538d5-803f-11ed-ab7e-8139573aad8f
last_name: Jethwa
orcid: 0000-0002-0404-4356
- first_name: Alice E.
full_name: Beardmore, Alice E.
last_name: Beardmore
- first_name: Teresa
full_name: Insinna, Teresa
last_name: Insinna
- first_name: Christopher A.
full_name: O'Keefe, Christopher A.
last_name: O'Keefe
- first_name: Peter A.A.
full_name: Klusener, Peter A.A.
last_name: Klusener
- first_name: Clare P.
full_name: Grey, Clare P.
last_name: Grey
- first_name: Dominic S.
full_name: Wright, Dominic S.
last_name: Wright
citation:
ama: Farag NL, Jethwa RB, Beardmore AE, et al. Triarylamines as catholytes in aqueous
organic redox flow batteries. ChemSusChem. 2023;16(13). doi:10.1002/cssc.202300128
apa: Farag, N. L., Jethwa, R. B., Beardmore, A. E., Insinna, T., O’Keefe, C. A.,
Klusener, P. A. A., … Wright, D. S. (2023). Triarylamines as catholytes in aqueous
organic redox flow batteries. ChemSusChem. Wiley. https://doi.org/10.1002/cssc.202300128
chicago: Farag, Nadia L., Rajesh B Jethwa, Alice E. Beardmore, Teresa Insinna, Christopher
A. O’Keefe, Peter A.A. Klusener, Clare P. Grey, and Dominic S. Wright. “Triarylamines
as Catholytes in Aqueous Organic Redox Flow Batteries.” ChemSusChem. Wiley,
2023. https://doi.org/10.1002/cssc.202300128.
ieee: N. L. Farag et al., “Triarylamines as catholytes in aqueous organic
redox flow batteries,” ChemSusChem, vol. 16, no. 13. Wiley, 2023.
ista: Farag NL, Jethwa RB, Beardmore AE, Insinna T, O’Keefe CA, Klusener PAA, Grey
CP, Wright DS. 2023. Triarylamines as catholytes in aqueous organic redox flow
batteries. ChemSusChem. 16(13), e202300128.
mla: Farag, Nadia L., et al. “Triarylamines as Catholytes in Aqueous Organic Redox
Flow Batteries.” ChemSusChem, vol. 16, no. 13, e202300128, Wiley, 2023,
doi:10.1002/cssc.202300128.
short: N.L. Farag, R.B. Jethwa, A.E. Beardmore, T. Insinna, C.A. O’Keefe, P.A.A.
Klusener, C.P. Grey, D.S. Wright, ChemSusChem 16 (2023).
date_created: 2023-05-21T22:01:05Z
date_published: 2023-07-06T00:00:00Z
date_updated: 2023-11-14T11:28:23Z
day: '06'
ddc:
- '540'
department:
- _id: StFr
doi: 10.1002/cssc.202300128
external_id:
isi:
- '000985051300001'
pmid:
- '36970847'
file:
- access_level: open_access
checksum: efa0713289995af83a2147b3e8e1d6a6
content_type: application/pdf
creator: dernst
date_created: 2023-11-14T11:27:16Z
date_updated: 2023-11-14T11:27:16Z
file_id: '14532'
file_name: 2023_ChemSusChem_Farag.pdf
file_size: 1168683
relation: main_file
success: 1
file_date_updated: 2023-11-14T11:27:16Z
has_accepted_license: '1'
intvolume: ' 16'
isi: 1
issue: '13'
language:
- iso: eng
month: '07'
oa: 1
oa_version: Published Version
pmid: 1
publication: ChemSusChem
publication_identifier:
eissn:
- 1864-564X
issn:
- 1864-5631
publication_status: published
publisher: Wiley
quality_controlled: '1'
scopus_import: '1'
status: public
title: Triarylamines as catholytes in aqueous organic redox flow batteries
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 16
year: '2023'
...
---
_id: '13044'
abstract:
- lang: eng
text: Singlet oxygen (1O2) formation is now recognised as a key aspect of non-aqueous
oxygen redox chemistry. For identifying 1O2, chemical trapping via 9,10-dimethylanthracene
(DMA) to form the endoperoxide (DMA-O2) has become the mainstay method due to
its sensitivity, selectivity, and ease of use. While DMA has been shown to be
selective for 1O2, rather than forming DMA-O2 with a wide variety of potentially
reactive O-containing species, false positives might hypothetically be obtained
in the presence of previously overlooked species. Here, we first give unequivocal
direct spectroscopic proof by the 1O2-specific near infrared (NIR) emission at
1270 nm for the previously proposed 1O2 formation pathways, which centre around
superoxide disproportionation. We then show that peroxocarbonates, common intermediates
in metal-O2 and metal carbonate electrochemistry, do not produce false-positive
DMA-O2. Moreover, we identify a previously unreported 1O2-forming pathway through
the reaction of CO2 with superoxide. Overall, we give unequivocal proof for 1O2
formation in non-aqueous oxygen redox and show that chemical trapping with DMA
is a reliable method to assess 1O2 formation.
article_processing_charge: No
article_type: original
author:
- first_name: Soumyadip
full_name: Mondal, Soumyadip
id: d25d21ef-dc8d-11ea-abe3-ec4576307f48
last_name: Mondal
- first_name: Rajesh B
full_name: Jethwa, Rajesh B
id: 4cc538d5-803f-11ed-ab7e-8139573aad8f
last_name: Jethwa
orcid: 0000-0002-0404-4356
- first_name: Bhargavi
full_name: Pant, Bhargavi
id: 50c64d4d-eb97-11eb-a6c2-d33e5e14f112
last_name: Pant
- first_name: Robert
full_name: Hauschild, Robert
id: 4E01D6B4-F248-11E8-B48F-1D18A9856A87
last_name: Hauschild
orcid: 0000-0001-9843-3522
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
citation:
ama: 'Mondal S, Jethwa RB, Pant B, Hauschild R, Freunberger SA. Singlet oxygen in
non-aqueous oxygen redox: Direct spectroscopic evidence for formation pathways
and reliability of chemical probes. Faraday Discussions. 2023. doi:10.1039/d3fd00088e'
apa: 'Mondal, S., Jethwa, R. B., Pant, B., Hauschild, R., & Freunberger, S.
A. (2023). Singlet oxygen in non-aqueous oxygen redox: Direct spectroscopic evidence
for formation pathways and reliability of chemical probes. Faraday Discussions.
Royal Society of Chemistry. https://doi.org/10.1039/d3fd00088e'
chicago: 'Mondal, Soumyadip, Rajesh B Jethwa, Bhargavi Pant, Robert Hauschild, and
Stefan Alexander Freunberger. “Singlet Oxygen in Non-Aqueous Oxygen Redox: Direct
Spectroscopic Evidence for Formation Pathways and Reliability of Chemical Probes.”
Faraday Discussions. Royal Society of Chemistry, 2023. https://doi.org/10.1039/d3fd00088e.'
ieee: 'S. Mondal, R. B. Jethwa, B. Pant, R. Hauschild, and S. A. Freunberger, “Singlet
oxygen in non-aqueous oxygen redox: Direct spectroscopic evidence for formation
pathways and reliability of chemical probes,” Faraday Discussions. Royal
Society of Chemistry, 2023.'
ista: 'Mondal S, Jethwa RB, Pant B, Hauschild R, Freunberger SA. 2023. Singlet oxygen
in non-aqueous oxygen redox: Direct spectroscopic evidence for formation pathways
and reliability of chemical probes. Faraday Discussions.'
mla: 'Mondal, Soumyadip, et al. “Singlet Oxygen in Non-Aqueous Oxygen Redox: Direct
Spectroscopic Evidence for Formation Pathways and Reliability of Chemical Probes.”
Faraday Discussions, Royal Society of Chemistry, 2023, doi:10.1039/d3fd00088e.'
short: S. Mondal, R.B. Jethwa, B. Pant, R. Hauschild, S.A. Freunberger, Faraday
Discussions (2023).
date_created: 2023-05-22T06:53:34Z
date_published: 2023-05-17T00:00:00Z
date_updated: 2023-12-13T11:19:07Z
day: '17'
department:
- _id: StFr
- _id: Bio
doi: 10.1039/d3fd00088e
external_id:
isi:
- '001070423500001'
isi: 1
keyword:
- Physical and Theoretical Chemistry
language:
- iso: eng
license: https://creativecommons.org/licenses/by-nc/4.0/
main_file_link:
- open_access: '1'
url: https://doi.org/10.1039/d3fd00088e
month: '05'
oa: 1
oa_version: Published Version
publication: Faraday Discussions
publication_identifier:
eissn:
- 1364-5498
issn:
- 1359-6640
publication_status: epub_ahead
publisher: Royal Society of Chemistry
quality_controlled: '1'
status: public
title: 'Singlet oxygen in non-aqueous oxygen redox: Direct spectroscopic evidence
for formation pathways and reliability of chemical probes'
tmp:
image: /images/cc_by_nc.png
legal_code_url: https://creativecommons.org/licenses/by-nc/4.0/legalcode
name: Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0)
short: CC BY-NC (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
year: '2023'
...
---
_id: '10813'
abstract:
- lang: eng
text: Redox mediators could catalyse otherwise slow and energy-inefficient cycling
of Li–S and Li–O2 batteries by shuttling electrons or holes between the electrode
and the solid insulating storage materials. For mediators to work efficiently
they need to oxidize the solid with fast kinetics but with the lowest possible
overpotential. However, the dependence of kinetics and overpotential is unclear,
which hinders informed improvement. Here, we find that when the redox potentials
of mediators are tuned via, for example, Li+ concentration in the electrolyte,
they exhibit distinct threshold potentials, where the kinetics accelerate several-fold
within a range as small as 10 mV. This phenomenon is independent of types of mediator
and electrolyte. The acceleration originates from the overpotentials required
to activate fast Li+/e− extraction and the following chemical step at specific
abundant surface facets. Efficient redox catalysis at insulating solids therefore
requires careful consideration of the surface conditions of the storage materials
and electrolyte-dependent redox potentials, which may be tuned by salt concentrations
or solvents.
acknowledgement: This work was financially supported by the National Natural Science
Foundation of China (grant nos. 51773092, 21975124, 11874254, 51802187 and U2030206).
It was further supported by Fujian science & technology innovation laboratory for
energy devices of China (21C-LAB), Key Research Project of Zhejiang Laboratory (grant
no. 2021PE0AC02) and the Cultivation Program for the Excellent Doctoral Dissertation
of Nanjing Tech University. S.A.F. is indebted to IST Austria for support.
article_processing_charge: No
article_type: original
author:
- first_name: Deqing
full_name: Cao, Deqing
last_name: Cao
- first_name: Xiaoxiao
full_name: Shen, Xiaoxiao
last_name: Shen
- first_name: Aiping
full_name: Wang, Aiping
last_name: Wang
- first_name: Fengjiao
full_name: Yu, Fengjiao
last_name: Yu
- first_name: Yuping
full_name: Wu, Yuping
last_name: Wu
- first_name: Siqi
full_name: Shi, Siqi
last_name: Shi
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Yuhui
full_name: Chen, Yuhui
last_name: Chen
citation:
ama: Cao D, Shen X, Wang A, et al. Threshold potentials for fast kinetics during
mediated redox catalysis of insulators in Li–O2 and Li–S batteries. Nature
Catalysis. 2022;5:193-201. doi:10.1038/s41929-022-00752-z
apa: Cao, D., Shen, X., Wang, A., Yu, F., Wu, Y., Shi, S., … Chen, Y. (2022). Threshold
potentials for fast kinetics during mediated redox catalysis of insulators in
Li–O2 and Li–S batteries. Nature Catalysis. Springer Nature. https://doi.org/10.1038/s41929-022-00752-z
chicago: Cao, Deqing, Xiaoxiao Shen, Aiping Wang, Fengjiao Yu, Yuping Wu, Siqi Shi,
Stefan Alexander Freunberger, and Yuhui Chen. “Threshold Potentials for Fast Kinetics
during Mediated Redox Catalysis of Insulators in Li–O2 and Li–S Batteries.” Nature
Catalysis. Springer Nature, 2022. https://doi.org/10.1038/s41929-022-00752-z.
ieee: D. Cao et al., “Threshold potentials for fast kinetics during mediated
redox catalysis of insulators in Li–O2 and Li–S batteries,” Nature Catalysis,
vol. 5. Springer Nature, pp. 193–201, 2022.
ista: Cao D, Shen X, Wang A, Yu F, Wu Y, Shi S, Freunberger SA, Chen Y. 2022. Threshold
potentials for fast kinetics during mediated redox catalysis of insulators in
Li–O2 and Li–S batteries. Nature Catalysis. 5, 193–201.
mla: Cao, Deqing, et al. “Threshold Potentials for Fast Kinetics during Mediated
Redox Catalysis of Insulators in Li–O2 and Li–S Batteries.” Nature Catalysis,
vol. 5, Springer Nature, 2022, pp. 193–201, doi:10.1038/s41929-022-00752-z.
short: D. Cao, X. Shen, A. Wang, F. Yu, Y. Wu, S. Shi, S.A. Freunberger, Y. Chen,
Nature Catalysis 5 (2022) 193–201.
date_created: 2022-03-04T07:50:10Z
date_published: 2022-03-03T00:00:00Z
date_updated: 2023-10-17T13:06:28Z
day: '03'
department:
- _id: StFr
doi: 10.1038/s41929-022-00752-z
external_id:
isi:
- '000763879400001'
intvolume: ' 5'
isi: 1
keyword:
- Process Chemistry and Technology
- Biochemistry
- Bioengineering
- Catalysis
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.21203/rs.3.rs-750965/v1
month: '03'
oa: 1
oa_version: Preprint
page: 193-201
publication: Nature Catalysis
publication_identifier:
issn:
- 2520-1158
publication_status: published
publisher: Springer Nature
quality_controlled: '1'
related_material:
record:
- id: '9978'
relation: earlier_version
status: public
scopus_import: '1'
status: public
title: Threshold potentials for fast kinetics during mediated redox catalysis of insulators
in Li–O2 and Li–S batteries
type: journal_article
user_id: 4359f0d1-fa6c-11eb-b949-802e58b17ae8
volume: 5
year: '2022'
...
---
_id: '12065'
abstract:
- lang: eng
text: Capacity, rate performance, and cycle life of aprotic Li–O2 batteries critically
depend on reversible electrodeposition of Li2O2. Current understanding states
surface-adsorbed versus solvated LiO2 controls Li2O2 growth as surface film or
as large particles. Herein, we show that Li2O2 forms across a wide range of electrolytes,
carbons, and current densities as particles via solution-mediated LiO2 disproportionation,
bringing into question the prevalence of any surface growth under practical conditions.
We describe a unified O2 reduction mechanism, which can explain all found capacity
relations and Li2O2 morphologies with exclusive solution discharge. Determining
particle morphology and achievable capacities are species mobilities, true areal
rate, and the degree of LiO2 association in solution. Capacity is conclusively
limited by mass transport through the tortuous Li2O2 rather than electron transport
through a passivating Li2O2 film. Provided that species mobilities and surface
growth are high, high capacities are also achieved with weakly solvating electrolytes,
which were previously considered prototypical for low capacity via surface growth.
acknowledged_ssus:
- _id: EM-Fac
- _id: M-Shop
acknowledgement: S.A.F. and C.P. are indebted to the European Research Council (ERC)
under the European Union’s Horizon 2020 research and innovation program (Grant Agreement
No. 636069). This project has received funding from the European Union’s Horizon
2020 research and innovation program under the Marie Skłodowska-Curie Grant NanoEvolution,
Grant Agreement No. 894042. S.A.F. and S.M. are indebted to Institute of Science
and Technology Austria (ISTA) for support. This research was supported by the Scientific
Service Units of ISTA through resources provided by the Electron Microscopy Facility
and the Miba Machine Shop. C.P. thanks Vanessa Wood (ETH Zürich) for her continuing
support.
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Christian
full_name: Prehal, Christian
last_name: Prehal
- first_name: Soumyadip
full_name: Mondal, Soumyadip
id: d25d21ef-dc8d-11ea-abe3-ec4576307f48
last_name: Mondal
- first_name: Ludek
full_name: Lovicar, Ludek
id: 36DB3A20-F248-11E8-B48F-1D18A9856A87
last_name: Lovicar
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
citation:
ama: Prehal C, Mondal S, Lovicar L, Freunberger SA. Exclusive solution discharge
in Li-O₂ batteries? ACS Energy Letters. 2022;7(9):3112-3119. doi:10.1021/acsenergylett.2c01711
apa: Prehal, C., Mondal, S., Lovicar, L., & Freunberger, S. A. (2022). Exclusive
solution discharge in Li-O₂ batteries? ACS Energy Letters. American Chemical
Society. https://doi.org/10.1021/acsenergylett.2c01711
chicago: Prehal, Christian, Soumyadip Mondal, Ludek Lovicar, and Stefan Alexander
Freunberger. “Exclusive Solution Discharge in Li-O₂ Batteries?” ACS Energy
Letters. American Chemical Society, 2022. https://doi.org/10.1021/acsenergylett.2c01711.
ieee: C. Prehal, S. Mondal, L. Lovicar, and S. A. Freunberger, “Exclusive solution
discharge in Li-O₂ batteries?,” ACS Energy Letters, vol. 7, no. 9. American
Chemical Society, pp. 3112–3119, 2022.
ista: Prehal C, Mondal S, Lovicar L, Freunberger SA. 2022. Exclusive solution discharge
in Li-O₂ batteries? ACS Energy Letters. 7(9), 3112–3119.
mla: Prehal, Christian, et al. “Exclusive Solution Discharge in Li-O₂ Batteries?”
ACS Energy Letters, vol. 7, no. 9, American Chemical Society, 2022, pp.
3112–19, doi:10.1021/acsenergylett.2c01711.
short: C. Prehal, S. Mondal, L. Lovicar, S.A. Freunberger, ACS Energy Letters 7
(2022) 3112–3119.
date_created: 2022-09-08T09:51:09Z
date_published: 2022-08-29T00:00:00Z
date_updated: 2023-08-03T13:47:56Z
day: '29'
ddc:
- '540'
department:
- _id: StFr
- _id: EM-Fac
doi: 10.1021/acsenergylett.2c01711
external_id:
isi:
- '000860787000001'
file:
- access_level: open_access
checksum: cf0bed3a2535c11d27244cd029dbc1d0
content_type: application/pdf
creator: dernst
date_created: 2023-01-20T08:43:51Z
date_updated: 2023-01-20T08:43:51Z
file_id: '12319'
file_name: 2022_ACSEnergyLetters_Prehal.pdf
file_size: 3827583
relation: main_file
success: 1
file_date_updated: 2023-01-20T08:43:51Z
has_accepted_license: '1'
intvolume: ' 7'
isi: 1
issue: '9'
language:
- iso: eng
month: '08'
oa: 1
oa_version: Published Version
page: 3112-3119
publication: ACS Energy Letters
publication_identifier:
eissn:
- 2380-8195
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Exclusive solution discharge in Li-O₂ batteries?
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 4359f0d1-fa6c-11eb-b949-802e58b17ae8
volume: 7
year: '2022'
...
---
_id: '12208'
abstract:
- lang: eng
text: The inadequate understanding of the mechanisms that reversibly convert molecular
sulfur (S) into lithium sulfide (Li2S) via soluble polysulfides
(PSs) formation impedes the development of high-performance lithium-sulfur (Li-S)
batteries with non-aqueous electrolyte solutions. Here, we use operando small
and wide angle X-ray scattering and operando small angle neutron scattering (SANS)
measurements to track the nucleation, growth and dissolution of solid deposits
from atomic to sub-micron scales during real-time Li-S cell operation. In particular,
stochastic modelling based on the SANS data allows quantifying the nanoscale phase
evolution during battery cycling. We show that next to nano-crystalline Li2S
the deposit comprises solid short-chain PSs particles. The analysis of the experimental
data suggests that initially, Li2S2
precipitates from the solution and then is partially converted via solid-state
electroreduction to Li2S. We further demonstrate that mass
transport, rather than electron transport through a thin passivating film, limits
the discharge capacity and rate performance in Li-S cells.
acknowledgement: "This project has received funding from the European Union’s Horizon
2020 research and innovation program under the Marie Skłodowska-Curie grant NanoEvolution,
grant agreement No 894042. The authors acknowledge the CERIC-ERIC Consortium for
the access to the Austrian SAXS beamline and TU Graz for support through the Lead
Project LP-03.\r\nLikewise, the use of SOMAPP Lab, a core facility supported by
the Austrian Federal Ministry of Education, Science and Research, the Graz University
of Technology, the University of Graz, and Anton Paar GmbH is acknowledged. In addition,
the authors acknowledge access to the D-22SANS beamline at the ILL neutron source.
Electron microscopy measurements were performed at the Scientific Scenter for Optical
and Electron Microscopy (ScopeM) of the Swiss Federal Institute of Technology. C.P.
and J.M.M. thank A. Senol for her support with the SANS\r\nbeamtime preparation.
S.D.T, A.V. and R.D. acknowledge the financial support by the Slovenian Research
Agency (ARRS) research core funding P2-0393 and P2-0423. Furthermore, A.V. acknowledge
the funding from the Slovenian Research Agency, research project Z2−1863.\r\nS.A.F.
is indebted to IST Austria for support. "
article_number: '6326'
article_processing_charge: No
article_type: original
author:
- first_name: Christian
full_name: Prehal, Christian
last_name: Prehal
- first_name: Jean-Marc
full_name: von Mentlen, Jean-Marc
last_name: von Mentlen
- first_name: Sara
full_name: Drvarič Talian, Sara
last_name: Drvarič Talian
- first_name: Alen
full_name: Vizintin, Alen
last_name: Vizintin
- first_name: Robert
full_name: Dominko, Robert
last_name: Dominko
- first_name: Heinz
full_name: Amenitsch, Heinz
last_name: Amenitsch
- first_name: Lionel
full_name: Porcar, Lionel
last_name: Porcar
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Vanessa
full_name: Wood, Vanessa
last_name: Wood
citation:
ama: Prehal C, von Mentlen J-M, Drvarič Talian S, et al. On the nanoscale structural
evolution of solid discharge products in lithium-sulfur batteries using operando
scattering. Nature Communications. 2022;13. doi:10.1038/s41467-022-33931-4
apa: Prehal, C., von Mentlen, J.-M., Drvarič Talian, S., Vizintin, A., Dominko,
R., Amenitsch, H., … Wood, V. (2022). On the nanoscale structural evolution of
solid discharge products in lithium-sulfur batteries using operando scattering.
Nature Communications. Springer Nature. https://doi.org/10.1038/s41467-022-33931-4
chicago: Prehal, Christian, Jean-Marc von Mentlen, Sara Drvarič Talian, Alen Vizintin,
Robert Dominko, Heinz Amenitsch, Lionel Porcar, Stefan Alexander Freunberger,
and Vanessa Wood. “On the Nanoscale Structural Evolution of Solid Discharge Products
in Lithium-Sulfur Batteries Using Operando Scattering.” Nature Communications.
Springer Nature, 2022. https://doi.org/10.1038/s41467-022-33931-4.
ieee: C. Prehal et al., “On the nanoscale structural evolution of solid discharge
products in lithium-sulfur batteries using operando scattering,” Nature Communications,
vol. 13. Springer Nature, 2022.
ista: Prehal C, von Mentlen J-M, Drvarič Talian S, Vizintin A, Dominko R, Amenitsch
H, Porcar L, Freunberger SA, Wood V. 2022. On the nanoscale structural evolution
of solid discharge products in lithium-sulfur batteries using operando scattering.
Nature Communications. 13, 6326.
mla: Prehal, Christian, et al. “On the Nanoscale Structural Evolution of Solid Discharge
Products in Lithium-Sulfur Batteries Using Operando Scattering.” Nature Communications,
vol. 13, 6326, Springer Nature, 2022, doi:10.1038/s41467-022-33931-4.
short: C. Prehal, J.-M. von Mentlen, S. Drvarič Talian, A. Vizintin, R. Dominko,
H. Amenitsch, L. Porcar, S.A. Freunberger, V. Wood, Nature Communications 13 (2022).
date_created: 2023-01-16T09:45:09Z
date_published: 2022-10-24T00:00:00Z
date_updated: 2023-08-04T09:15:31Z
day: '24'
ddc:
- '540'
department:
- _id: StFr
doi: 10.1038/s41467-022-33931-4
external_id:
isi:
- '000871563700006'
pmid:
- '36280671'
file:
- access_level: open_access
checksum: 5034336dbf0f860030ef745c08df9e0e
content_type: application/pdf
creator: dernst
date_created: 2023-01-27T07:19:11Z
date_updated: 2023-01-27T07:19:11Z
file_id: '12411'
file_name: 2022_NatureCommunications_Prehal.pdf
file_size: 4216931
relation: main_file
success: 1
file_date_updated: 2023-01-27T07:19:11Z
has_accepted_license: '1'
intvolume: ' 13'
isi: 1
keyword:
- General Physics and Astronomy
- General Biochemistry
- Genetics and Molecular Biology
- General Chemistry
- Multidisciplinary
language:
- iso: eng
month: '10'
oa: 1
oa_version: Published Version
pmid: 1
publication: Nature Communications
publication_identifier:
issn:
- 2041-1723
publication_status: published
publisher: Springer Nature
quality_controlled: '1'
scopus_import: '1'
status: public
title: On the nanoscale structural evolution of solid discharge products in lithium-sulfur
batteries using operando scattering
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 4359f0d1-fa6c-11eb-b949-802e58b17ae8
volume: 13
year: '2022'
...
---
_id: '12227'
abstract:
- lang: eng
text: Polydicyclopentadiene (pDCPD), a thermoset with excellent mechanical properties,
has enormous potential as a lightweight, tough, and stable matrix material owing
to its highly cross-linked macromolecular network. This work describes generating
pDCPD-based foams and hierarchically porous carbons derived therefrom by combining
ring-opening metathesis polymerization (ROMP) of DCPD, high internal phase emulsions
(HIPEs) as structural templates, and subsequent carbonization. The structure and
function of the carbon foams were characterized and discussed in detail using
scanning electron, transmission electron, or atomic force microscopy (SEM, TEM,
AFM), electron energy-loss spectroscopy (TEM-EELS), N2 sorption, and analyses
of electrical conductivity as well as mechanical properties. The resulting materials
exhibited uniform, shape-retaining shrinkage of only ∼1/3 after carbonization.
No structural failure was observed even when the pDCPD precursor foams were heated
to 1400 °C. Instead, the high porosity, void size, and 3D interconnectivity were
fully preserved, and the void diameters could be adjusted between 87 and 2.5 μm.
Moreover, foams have a carbon content >97%, an electronic conductivity of up to
2800 S·m–1, a Young’s modulus of up to 2.1 GPa, and a specific surface area of
up to 1200 m2·g–1. Surprisingly, the pDCPD foams were carbonized into shapes other
than monoliths, such as 10’s of micron thick membranes or foamy coatings adhered
to a metal foil or grid substrate. The latter coatings even adhere upon bending.
Finally, as a use case, carbonized foams were applied as porous cathodes for Li–O2
batteries where the foams show a favorable combination of porosity, active surface
area, and pore size for outstanding capacity.
acknowledgement: S.K. acknowledges the financial support from the Slovenian Research
Agency (grants P1-0021, P2-0150). Support by Graz University of Technology (LP-03
– Porous Materials@Work) and from VARTA Innovation GmbH is kindly acknowledged.
We thank Umicore for providing the initiator and Matjaž Mazaj (National Institute
of Chemistry, Ljubljana) and Karel Jerabek (Czech Academy of Sciences) for measurements
and fruitful discussions. S.A.F. is indebted to the Austrian Federal Ministry of
Science, Research and Economy; the Austrian Research Promotion Agency (Grant No.
845364); and ISTA for support.
article_processing_charge: No
article_type: original
author:
- first_name: Sebastijan
full_name: Kovačič, Sebastijan
last_name: Kovačič
- first_name: Bettina
full_name: Schafzahl, Bettina
last_name: Schafzahl
- first_name: Nadejda B.
full_name: Matsko, Nadejda B.
last_name: Matsko
- first_name: Katharina
full_name: Gruber, Katharina
last_name: Gruber
- first_name: Martin
full_name: Schmuck, Martin
last_name: Schmuck
- first_name: Stefan
full_name: Koller, Stefan
last_name: Koller
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Christian
full_name: Slugovc, Christian
last_name: Slugovc
citation:
ama: 'Kovačič S, Schafzahl B, Matsko NB, et al. Carbon foams via ring-opening metathesis
polymerization of emulsion templates: A facile method to make carbon current collectors
for battery applications. ACS Applied Energy Materials. 2022;5(11):14381-14390.
doi:10.1021/acsaem.2c02787'
apa: 'Kovačič, S., Schafzahl, B., Matsko, N. B., Gruber, K., Schmuck, M., Koller,
S., … Slugovc, C. (2022). Carbon foams via ring-opening metathesis polymerization
of emulsion templates: A facile method to make carbon current collectors for battery
applications. ACS Applied Energy Materials. American Chemical Society.
https://doi.org/10.1021/acsaem.2c02787'
chicago: 'Kovačič, Sebastijan, Bettina Schafzahl, Nadejda B. Matsko, Katharina Gruber,
Martin Schmuck, Stefan Koller, Stefan Alexander Freunberger, and Christian Slugovc.
“Carbon Foams via Ring-Opening Metathesis Polymerization of Emulsion Templates:
A Facile Method to Make Carbon Current Collectors for Battery Applications.” ACS
Applied Energy Materials. American Chemical Society, 2022. https://doi.org/10.1021/acsaem.2c02787.'
ieee: 'S. Kovačič et al., “Carbon foams via ring-opening metathesis polymerization
of emulsion templates: A facile method to make carbon current collectors for battery
applications,” ACS Applied Energy Materials, vol. 5, no. 11. American Chemical
Society, pp. 14381–14390, 2022.'
ista: 'Kovačič S, Schafzahl B, Matsko NB, Gruber K, Schmuck M, Koller S, Freunberger
SA, Slugovc C. 2022. Carbon foams via ring-opening metathesis polymerization of
emulsion templates: A facile method to make carbon current collectors for battery
applications. ACS Applied Energy Materials. 5(11), 14381–14390.'
mla: 'Kovačič, Sebastijan, et al. “Carbon Foams via Ring-Opening Metathesis Polymerization
of Emulsion Templates: A Facile Method to Make Carbon Current Collectors for Battery
Applications.” ACS Applied Energy Materials, vol. 5, no. 11, American Chemical
Society, 2022, pp. 14381–90, doi:10.1021/acsaem.2c02787.'
short: S. Kovačič, B. Schafzahl, N.B. Matsko, K. Gruber, M. Schmuck, S. Koller,
S.A. Freunberger, C. Slugovc, ACS Applied Energy Materials 5 (2022) 14381–14390.
date_created: 2023-01-16T09:48:53Z
date_published: 2022-10-16T00:00:00Z
date_updated: 2023-08-04T09:27:32Z
day: '16'
ddc:
- '540'
department:
- _id: StFr
doi: 10.1021/acsaem.2c02787
external_id:
isi:
- '000875635900001'
file:
- access_level: open_access
checksum: 572d15c250ab83d44f4e2c3aeb5f7388
content_type: application/pdf
creator: dernst
date_created: 2023-01-27T09:09:15Z
date_updated: 2023-01-27T09:09:15Z
file_id: '12420'
file_name: 2022_AppliedEnergyMaterials_Kovacic.pdf
file_size: 13105589
relation: main_file
success: 1
file_date_updated: 2023-01-27T09:09:15Z
has_accepted_license: '1'
intvolume: ' 5'
isi: 1
issue: '11'
keyword:
- Electrical and Electronic Engineering
- Materials Chemistry
- Electrochemistry
- Energy Engineering and Power Technology
- Chemical Engineering (miscellaneous)
language:
- iso: eng
month: '10'
oa: 1
oa_version: Published Version
page: 14381-14390
publication: ACS Applied Energy Materials
publication_identifier:
issn:
- 2574-0962
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'Carbon foams via ring-opening metathesis polymerization of emulsion templates:
A facile method to make carbon current collectors for battery applications'
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: 4359f0d1-fa6c-11eb-b949-802e58b17ae8
volume: 5
year: '2022'
...
---
_id: '9113'
abstract:
- lang: eng
text: “Hydrogen economy” could enable a carbon-neutral sustainable energy chain.
However, issues with safety, storage, and transport of molecular hydrogen impede
its realization. Alcohols as liquid H2 carriers could be enablers, but state-of-the-art
reforming is difficult, requiring high temperatures >200 °C and pressures >25
bar, and the resulting H2 is carbonized beyond tolerance levels for direct use
in fuel cells. Here, we demonstrate ambient temperature and pressure alcohol reforming
in a fuel cell (ARFC) with a simultaneous electrical power output. The alcohol
is oxidized at the alkaline anode, where the resulting CO2 is sequestrated as
carbonate. Carbon-free H2 is liberated at the acidic cathode. The neutralization
energy between the alkaline anode and the acidic cathode drives the process, particularly
the unusually high entropy gain (1.27-fold ΔH). The significantly positive temperature
coefficient of the resulting electromotive force allows us to harvest a large
fraction of the output energy from the surrounding, achieving a thermodynamic
efficiency as high as 2.27. MoS2 as the cathode catalyst allows alcohol reforming
even under open-air conditions, a challenge that state-of-the-art alcohol reforming
failed to overcome. We further show reforming of a wide range of alcohols. The
ARFC offers an unprecedented route toward hydrogen economy as CO2 is simultaneously
captured and pure H2 produced at mild conditions.
acknowledgement: M.O.T. acknowledges DST/TMD/HFC/2 K18/58, DST-SERB, MHRD fast track,
and DST Nanomission forfinancialassistance. Z.M.B. acknowledges CSIR-SRF fellowship
fromMHRD, India. S.A.F. acknowledges support from IST Austria.
article_processing_charge: No
article_type: original
author:
- first_name: Zahid Manzoor
full_name: Manzoor Bhat, Zahid Manzoor
last_name: Manzoor Bhat
- first_name: Ravikumar
full_name: Thimmappa, Ravikumar
last_name: Thimmappa
- first_name: 'Neethu Christudas '
full_name: 'Dargily, Neethu Christudas '
last_name: Dargily
- first_name: 'Abdul '
full_name: 'Raafik, Abdul '
last_name: Raafik
- first_name: 'Alagar Raja '
full_name: 'Kottaichamy, Alagar Raja '
last_name: Kottaichamy
- first_name: 'Mruthyunjayachari Chattanahalli '
full_name: 'Devendrachari, Mruthyunjayachari Chattanahalli '
last_name: Devendrachari
- first_name: Mahesh
full_name: Itagi, Mahesh
last_name: Itagi
- first_name: Harish
full_name: ' Makri Nimbegondi Kotresh, Harish'
last_name: ' Makri Nimbegondi Kotresh'
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: 'Musthafa '
full_name: 'Ottakam Thotiyl, Musthafa '
last_name: Ottakam Thotiyl
citation:
ama: Manzoor Bhat ZM, Thimmappa R, Dargily NC, et al. Ambient condition alcohol
reforming to hydrogen with electricity output. ACS Sustainable Chemistry and
Engineering. 2021;9(8):3104-3111. doi:10.1021/acssuschemeng.0c07547
apa: Manzoor Bhat, Z. M., Thimmappa, R., Dargily, N. C., Raafik, A., Kottaichamy,
A. R., Devendrachari, M. C., … Ottakam Thotiyl, M. (2021). Ambient condition alcohol
reforming to hydrogen with electricity output. ACS Sustainable Chemistry and
Engineering. American Chemical Society. https://doi.org/10.1021/acssuschemeng.0c07547
chicago: Manzoor Bhat, Zahid Manzoor, Ravikumar Thimmappa, Neethu Christudas Dargily,
Abdul Raafik, Alagar Raja Kottaichamy, Mruthyunjayachari Chattanahalli Devendrachari,
Mahesh Itagi, Harish Makri Nimbegondi Kotresh, Stefan Alexander Freunberger,
and Musthafa Ottakam Thotiyl. “Ambient Condition Alcohol Reforming to Hydrogen
with Electricity Output.” ACS Sustainable Chemistry and Engineering. American
Chemical Society, 2021. https://doi.org/10.1021/acssuschemeng.0c07547.
ieee: Z. M. Manzoor Bhat et al., “Ambient condition alcohol reforming to
hydrogen with electricity output,” ACS Sustainable Chemistry and Engineering,
vol. 9, no. 8. American Chemical Society, pp. 3104–3111, 2021.
ista: Manzoor Bhat ZM, Thimmappa R, Dargily NC, Raafik A, Kottaichamy AR, Devendrachari
MC, Itagi M, Makri Nimbegondi Kotresh H, Freunberger SA, Ottakam Thotiyl M. 2021.
Ambient condition alcohol reforming to hydrogen with electricity output. ACS Sustainable
Chemistry and Engineering. 9(8), 3104–3111.
mla: Manzoor Bhat, Zahid Manzoor, et al. “Ambient Condition Alcohol Reforming to
Hydrogen with Electricity Output.” ACS Sustainable Chemistry and Engineering,
vol. 9, no. 8, American Chemical Society, 2021, pp. 3104–11, doi:10.1021/acssuschemeng.0c07547.
short: Z.M. Manzoor Bhat, R. Thimmappa, N.C. Dargily, A. Raafik, A.R. Kottaichamy,
M.C. Devendrachari, M. Itagi, H. Makri Nimbegondi Kotresh, S.A. Freunberger,
M. Ottakam Thotiyl, ACS Sustainable Chemistry and Engineering 9 (2021) 3104–3111.
date_created: 2021-02-12T09:20:18Z
date_published: 2021-02-11T00:00:00Z
date_updated: 2023-08-07T13:43:19Z
day: '11'
department:
- _id: StFr
doi: 10.1021/acssuschemeng.0c07547
external_id:
isi:
- '000625460400010'
intvolume: ' 9'
isi: 1
issue: '8'
language:
- iso: eng
month: '02'
oa_version: None
page: 3104-3111
publication: ACS Sustainable Chemistry and Engineering
publication_identifier:
eissn:
- 2168-0485
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Ambient condition alcohol reforming to hydrogen with electricity output
type: journal_article
user_id: 4359f0d1-fa6c-11eb-b949-802e58b17ae8
volume: 9
year: '2021'
...
---
_id: '9250'
abstract:
- lang: eng
text: Aprotic alkali metal–O2 batteries face two major obstacles to their chemistry
occurring efficiently, the insulating nature of the formed alkali superoxides/peroxides
and parasitic reactions that are caused by the highly reactive singlet oxygen
(1O2). Redox mediators are recognized to be key for improving rechargeability.
However, it is unclear how they affect 1O2 formation, which hinders strategies
for their improvement. Here we clarify the mechanism of mediated peroxide and
superoxide oxidation and thus explain how redox mediators either enhance or suppress
1O2 formation. We show that charging commences with peroxide oxidation to a superoxide
intermediate and that redox potentials above ~3.5 V versus Li/Li+ drive 1O2 evolution
from superoxide oxidation, while disproportionation always generates some 1O2.
We find that 1O2 suppression requires oxidation to be faster than the generation
of 1O2 from disproportionation. Oxidation rates decrease with growing driving
force following Marcus inverted-region behaviour, establishing a region of maximum
rate.
acknowledged_ssus:
- _id: M-Shop
acknowledgement: S.A.F. is indebted to the European Research Council (ERC) under the
European Union’s Horizon 2020 research and innovation programme (grant agreement
No. 636069) as well as IST Austria. O.F thanks the French National Research Agency
(STORE-EX Labex Project ANR-10-LABX-76-01). We thank EL-Cell GmbH (Hamburg, Germany)
for the pressure test cell. We thank R. Saf for help with the mass spectrometry,
J. Schlegl for manufacturing instrumentation, M. Winkler of Acib GmbH, G. Strohmeier
and R. Fürst for HPLC measurements and S. Mondal and S. Stadlbauer for kinetic measurements.
article_processing_charge: No
article_type: original
author:
- first_name: Yann K.
full_name: Petit, Yann K.
last_name: Petit
- first_name: Eléonore
full_name: Mourad, Eléonore
last_name: Mourad
- first_name: Christian
full_name: Prehal, Christian
last_name: Prehal
- first_name: Christian
full_name: Leypold, Christian
last_name: Leypold
- first_name: Andreas
full_name: Windischbacher, Andreas
last_name: Windischbacher
- first_name: Daniel
full_name: Mijailovic, Daniel
last_name: Mijailovic
- first_name: Christian
full_name: Slugovc, Christian
last_name: Slugovc
- first_name: Sergey M.
full_name: Borisov, Sergey M.
last_name: Borisov
- first_name: Egbert
full_name: Zojer, Egbert
last_name: Zojer
- first_name: Sergio
full_name: Brutti, Sergio
last_name: Brutti
- first_name: Olivier
full_name: Fontaine, Olivier
last_name: Fontaine
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
citation:
ama: Petit YK, Mourad E, Prehal C, et al. Mechanism of mediated alkali peroxide
oxidation and triplet versus singlet oxygen formation. Nature Chemistry.
2021;13(5):465-471. doi:10.1038/s41557-021-00643-z
apa: Petit, Y. K., Mourad, E., Prehal, C., Leypold, C., Windischbacher, A., Mijailovic,
D., … Freunberger, S. A. (2021). Mechanism of mediated alkali peroxide oxidation
and triplet versus singlet oxygen formation. Nature Chemistry. Springer
Nature. https://doi.org/10.1038/s41557-021-00643-z
chicago: Petit, Yann K., Eléonore Mourad, Christian Prehal, Christian Leypold, Andreas
Windischbacher, Daniel Mijailovic, Christian Slugovc, et al. “Mechanism of Mediated
Alkali Peroxide Oxidation and Triplet versus Singlet Oxygen Formation.” Nature
Chemistry. Springer Nature, 2021. https://doi.org/10.1038/s41557-021-00643-z.
ieee: Y. K. Petit et al., “Mechanism of mediated alkali peroxide oxidation
and triplet versus singlet oxygen formation,” Nature Chemistry, vol. 13,
no. 5. Springer Nature, pp. 465–471, 2021.
ista: Petit YK, Mourad E, Prehal C, Leypold C, Windischbacher A, Mijailovic D, Slugovc
C, Borisov SM, Zojer E, Brutti S, Fontaine O, Freunberger SA. 2021. Mechanism
of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation.
Nature Chemistry. 13(5), 465–471.
mla: Petit, Yann K., et al. “Mechanism of Mediated Alkali Peroxide Oxidation and
Triplet versus Singlet Oxygen Formation.” Nature Chemistry, vol. 13, no.
5, Springer Nature, 2021, pp. 465–71, doi:10.1038/s41557-021-00643-z.
short: Y.K. Petit, E. Mourad, C. Prehal, C. Leypold, A. Windischbacher, D. Mijailovic,
C. Slugovc, S.M. Borisov, E. Zojer, S. Brutti, O. Fontaine, S.A. Freunberger,
Nature Chemistry 13 (2021) 465–471.
date_created: 2021-03-16T11:12:20Z
date_published: 2021-03-15T00:00:00Z
date_updated: 2023-09-05T15:34:44Z
day: '15'
ddc:
- '540'
department:
- _id: StFr
doi: 10.1038/s41557-021-00643-z
external_id:
isi:
- '000629296400001'
pmid:
- '33723377'
file:
- access_level: open_access
checksum: 3ee3f8dd79ed1b7bb0929fce184c8012
content_type: application/pdf
creator: dernst
date_created: 2021-03-22T11:46:00Z
date_updated: 2021-09-16T22:30:03Z
embargo: 2021-09-15
file_id: '9276'
file_name: 2021_NatureChem_Petit_acceptedVersion.pdf
file_size: 1811448
relation: main_file
file_date_updated: 2021-09-16T22:30:03Z
has_accepted_license: '1'
intvolume: ' 13'
isi: 1
issue: '5'
keyword:
- General Chemistry
- General Chemical Engineering
language:
- iso: eng
month: '03'
oa: 1
oa_version: Submitted Version
page: 465-471
pmid: 1
publication: Nature Chemistry
publication_identifier:
eissn:
- 1755-4349
issn:
- 1755-4330
publication_status: published
publisher: Springer Nature
quality_controlled: '1'
scopus_import: '1'
status: public
title: Mechanism of mediated alkali peroxide oxidation and triplet versus singlet
oxygen formation
type: journal_article
user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1
volume: 13
year: '2021'
...
---
_id: '9301'
abstract:
- lang: eng
text: Electrodepositing insulating lithium peroxide (Li2O2) is the key process during
discharge of aprotic Li–O2 batteries and determines rate, capacity, and reversibility.
Current understanding states that the partition between surface adsorbed and dissolved
lithium superoxide governs whether Li2O2 grows as a conformal surface film or
larger particles, leading to low or high capacities, respectively. However, better
understanding governing factors for Li2O2 packing density and capacity requires
structural sensitive in situ metrologies. Here, we establish in situ small- and
wide-angle X-ray scattering (SAXS/WAXS) as a suitable method to record the Li2O2
phase evolution with atomic to submicrometer resolution during cycling a custom-built
in situ Li–O2 cell. Combined with sophisticated data analysis, SAXS allows retrieving
rich quantitative structural information from complex multiphase systems. Surprisingly,
we find that features are absent that would point at a Li2O2 surface film formed
via two consecutive electron transfers, even in poorly solvating electrolytes
thought to be prototypical for surface growth. All scattering data can be modeled
by stacks of thin Li2O2 platelets potentially forming large toroidal particles.
Li2O2 solution growth is further justified by rotating ring-disk electrode measurements
and electron microscopy. Higher discharge overpotentials lead to smaller Li2O2
particles, but there is no transition to an electronically passivating, conformal
Li2O2 coating. Hence, mass transport of reactive species rather than electronic
transport through a Li2O2 film limits the discharge capacity. Provided that species
mobilities and carbon surface areas are high, this allows for high discharge capacities
even in weakly solvating electrolytes. The currently accepted Li–O2 reaction mechanism
ought to be reconsidered.
acknowledged_ssus:
- _id: EM-Fac
acknowledgement: S.A.F. and C.P. are indebted to the European Research Council under
the European Union's Horizon 2020 research and innovation program (Grant Agreement
No. 636069), the Austrian Federal Ministry of Science, Research and Economy, and
the Austrian Research Promotion Agency (Grant No. 845364). We acknowledge A. Zankel
and H. Schroettner for support with SEM measurements. C.P. thanks N. Kostoglou,
C. Koczwara, M. Hartmann, and M. Burian for discussions on gas sorption analysis,
C++ programming, Monte Carlo modeling, and in situ SAXS experiments, respectively.
We thank S. Stadlbauer for help with Karl Fischer titration, R. Riccò for gas sorption
measurements, and acknowledge Graz University of Technology for support through
the Lead Project LP-03. Likewise, the use of SOMAPP Lab, a core facility supported
by the Austrian Federal Ministry of Education, Science and Research, the Graz University
of Technology, the University of Graz, and Anton Paar GmbH is acknowledged. S.A.F.
is indebted to Institute of Science and Technology Austria (IST Austria) for support.
This research was supported by the Scientific Service Units of IST Austria through
resources provided by the Electron Microscopy Facility.
article_number: e2021893118
article_processing_charge: No
article_type: original
author:
- first_name: Christian
full_name: Prehal, Christian
last_name: Prehal
- first_name: Aleksej
full_name: Samojlov, Aleksej
last_name: Samojlov
- first_name: Manfred
full_name: Nachtnebel, Manfred
last_name: Nachtnebel
- first_name: Ludek
full_name: Lovicar, Ludek
id: 36DB3A20-F248-11E8-B48F-1D18A9856A87
last_name: Lovicar
orcid: 0000-0001-6206-4200
- first_name: Manfred
full_name: Kriechbaum, Manfred
last_name: Kriechbaum
- first_name: Heinz
full_name: Amenitsch, Heinz
last_name: Amenitsch
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
citation:
ama: Prehal C, Samojlov A, Nachtnebel M, et al. In situ small-angle X-ray scattering
reveals solution phase discharge of Li–O2 batteries with weakly solvating electrolytes.
Proceedings of the National Academy of Sciences. 2021;118(14). doi:10.1073/pnas.2021893118
apa: Prehal, C., Samojlov, A., Nachtnebel, M., Lovicar, L., Kriechbaum, M., Amenitsch,
H., & Freunberger, S. A. (2021). In situ small-angle X-ray scattering reveals
solution phase discharge of Li–O2 batteries with weakly solvating electrolytes.
Proceedings of the National Academy of Sciences. National Academy of Sciences.
https://doi.org/10.1073/pnas.2021893118
chicago: Prehal, Christian, Aleksej Samojlov, Manfred Nachtnebel, Ludek Lovicar,
Manfred Kriechbaum, Heinz Amenitsch, and Stefan Alexander Freunberger. “In Situ
Small-Angle X-Ray Scattering Reveals Solution Phase Discharge of Li–O2 Batteries
with Weakly Solvating Electrolytes.” Proceedings of the National Academy of
Sciences. National Academy of Sciences, 2021. https://doi.org/10.1073/pnas.2021893118.
ieee: C. Prehal et al., “In situ small-angle X-ray scattering reveals solution
phase discharge of Li–O2 batteries with weakly solvating electrolytes,” Proceedings
of the National Academy of Sciences, vol. 118, no. 14. National Academy of
Sciences, 2021.
ista: Prehal C, Samojlov A, Nachtnebel M, Lovicar L, Kriechbaum M, Amenitsch H,
Freunberger SA. 2021. In situ small-angle X-ray scattering reveals solution phase
discharge of Li–O2 batteries with weakly solvating electrolytes. Proceedings of
the National Academy of Sciences. 118(14), e2021893118.
mla: Prehal, Christian, et al. “In Situ Small-Angle X-Ray Scattering Reveals Solution
Phase Discharge of Li–O2 Batteries with Weakly Solvating Electrolytes.” Proceedings
of the National Academy of Sciences, vol. 118, no. 14, e2021893118, National
Academy of Sciences, 2021, doi:10.1073/pnas.2021893118.
short: C. Prehal, A. Samojlov, M. Nachtnebel, L. Lovicar, M. Kriechbaum, H. Amenitsch,
S.A. Freunberger, Proceedings of the National Academy of Sciences 118 (2021).
date_created: 2021-03-31T07:00:01Z
date_published: 2021-04-06T00:00:00Z
date_updated: 2023-09-05T13:27:18Z
day: '06'
department:
- _id: StFr
- _id: EM-Fac
doi: 10.1073/pnas.2021893118
external_id:
isi:
- '000637398300050'
intvolume: ' 118'
isi: 1
issue: '14'
keyword:
- small-angle X-ray scattering
- oxygen reduction
- disproportionation
- Li-air battery
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://doi.org/10.26434/chemrxiv.11447775
month: '04'
oa: 1
oa_version: Preprint
publication: Proceedings of the National Academy of Sciences
publication_identifier:
eissn:
- 1091-6490
issn:
- 0027-8424
publication_status: published
publisher: National Academy of Sciences
quality_controlled: '1'
status: public
title: In situ small-angle X-ray scattering reveals solution phase discharge of Li–O2
batteries with weakly solvating electrolytes
type: journal_article
user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1
volume: 118
year: '2021'
...
---
_id: '9447'
abstract:
- lang: eng
text: 'Lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) based water-in-salt electrolytes
(WiSEs) has recently emerged as a new promising class of electrolytes, primarily
owing to their wide electrochemical stability windows (~3–4 V), that by far exceed
the thermodynamic stability window of water (1.23 V). Upon increasing the salt
concentration towards superconcentration the onset of the oxygen evolution reaction
(OER) shifts more significantly than the hydrogen evolution reaction (HER) does.
The OER shift has been explained by the accumulation of hydrophobic anions blocking
water access to the electrode surface, hence by double layer theory. Here we demonstrate
that the processes during oxidation are much more complex, involving OER, carbon
and salt decomposition by OER intermediates, and salt precipitation upon local
oversaturation. The positive shift in the onset potential of oxidation currents
was elucidated by combining several advanced analysis techniques: rotating ring-disk
electrode voltammetry, online electrochemical mass spectrometry, and X-ray photoelectron
spectroscopy, using both dilute and superconcentrated electrolytes. The results
demonstrate the importance of reactive OER intermediates and surface films for
electrolyte and electrode stability and motivate further studies of the nature
of the electrode.'
article_number: '050550'
article_processing_charge: No
author:
- first_name: Marion
full_name: Maffre, Marion
last_name: Maffre
- first_name: Roza
full_name: Bouchal, Roza
last_name: Bouchal
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Niklas
full_name: Lindahl, Niklas
last_name: Lindahl
- first_name: Patrik
full_name: Johansson, Patrik
last_name: Johansson
- first_name: Frédéric
full_name: Favier, Frédéric
last_name: Favier
- first_name: Olivier
full_name: Fontaine, Olivier
last_name: Fontaine
- first_name: Daniel
full_name: Bélanger, Daniel
last_name: Bélanger
citation:
ama: Maffre M, Bouchal R, Freunberger SA, et al. Investigation of electrochemical
and chemical processes occurring at positive potentials in “Water-in-Salt” electrolytes.
Journal of The Electrochemical Society. 2021;168(5). doi:10.1149/1945-7111/ac0300
apa: Maffre, M., Bouchal, R., Freunberger, S. A., Lindahl, N., Johansson, P., Favier,
F., … Bélanger, D. (2021). Investigation of electrochemical and chemical processes
occurring at positive potentials in “Water-in-Salt” electrolytes. Journal of
The Electrochemical Society. IOP Publishing. https://doi.org/10.1149/1945-7111/ac0300
chicago: Maffre, Marion, Roza Bouchal, Stefan Alexander Freunberger, Niklas Lindahl,
Patrik Johansson, Frédéric Favier, Olivier Fontaine, and Daniel Bélanger. “Investigation
of Electrochemical and Chemical Processes Occurring at Positive Potentials in
‘Water-in-Salt’ Electrolytes.” Journal of The Electrochemical Society.
IOP Publishing, 2021. https://doi.org/10.1149/1945-7111/ac0300.
ieee: M. Maffre et al., “Investigation of electrochemical and chemical processes
occurring at positive potentials in ‘Water-in-Salt’ electrolytes,” Journal
of The Electrochemical Society, vol. 168, no. 5. IOP Publishing, 2021.
ista: Maffre M, Bouchal R, Freunberger SA, Lindahl N, Johansson P, Favier F, Fontaine
O, Bélanger D. 2021. Investigation of electrochemical and chemical processes occurring
at positive potentials in “Water-in-Salt” electrolytes. Journal of The Electrochemical
Society. 168(5), 050550.
mla: Maffre, Marion, et al. “Investigation of Electrochemical and Chemical Processes
Occurring at Positive Potentials in ‘Water-in-Salt’ Electrolytes.” Journal
of The Electrochemical Society, vol. 168, no. 5, 050550, IOP Publishing, 2021,
doi:10.1149/1945-7111/ac0300.
short: M. Maffre, R. Bouchal, S.A. Freunberger, N. Lindahl, P. Johansson, F. Favier,
O. Fontaine, D. Bélanger, Journal of The Electrochemical Society 168 (2021).
date_created: 2021-06-03T09:58:38Z
date_published: 2021-05-01T00:00:00Z
date_updated: 2023-09-05T13:25:30Z
day: '01'
department:
- _id: StFr
doi: 10.1149/1945-7111/ac0300
external_id:
isi:
- '000657724200001'
intvolume: ' 168'
isi: 1
issue: '5'
keyword:
- Renewable Energy
- Sustainability and the Environment
- Electrochemistry
- Materials Chemistry
- Electronic
- Optical and Magnetic Materials
- Surfaces
- Coatings and Films
- Condensed Matter Physics
language:
- iso: eng
month: '05'
oa_version: None
publication: Journal of The Electrochemical Society
publication_identifier:
eissn:
- 1945-7111
issn:
- 0013-4651
publication_status: published
publisher: IOP Publishing
quality_controlled: '1'
status: public
title: Investigation of electrochemical and chemical processes occurring at positive
potentials in “Water-in-Salt” electrolytes
type: journal_article
user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1
volume: 168
year: '2021'
...
---
_id: '9978'
abstract:
- lang: eng
text: Redox mediators could catalyse otherwise slow and energy-inefficient cycling
of Li-S and Li-O 2 batteries by shuttling electrons/holes between the electrode
and the solid insulating storage materials. For mediators to work efficiently
they need to oxidize the solid with fast kinetics yet the lowest possible overpotential.
Here, we found that when the redox potentials of mediators are tuned via, e.g.,
Li + concentration in the electrolyte, they exhibit distinct threshold potentials,
where the kinetics accelerate several-fold within a range as small as 10 mV. This
phenomenon is independent of types of mediators and electrolyte. The acceleration
originates from the overpotentials required to activate fast Li + /e – extraction
and the following chemical step at specific abundant surface facets. Efficient
redox catalysis at insulating solids requires therefore carefully considering
the surface conditions of the storage materials and electrolyte-dependent redox
potentials, which may be tuned by salt concentrations or solvents.
acknowledgement: 'This work was financially supported by the National Natural Science
Foundation of China (51773092, 21975124, 11874254, 51802187, U2030206). S.A.F. is
indebted to IST Austria for support. '
article_processing_charge: No
author:
- first_name: Deqing
full_name: Cao, Deqing
last_name: Cao
- first_name: Xiaoxiao
full_name: Shen, Xiaoxiao
last_name: Shen
- first_name: Aiping
full_name: Wang, Aiping
last_name: Wang
- first_name: Fengjiao
full_name: Yu, Fengjiao
last_name: Yu
- first_name: Yuping
full_name: Wu, Yuping
last_name: Wu
- first_name: Siqi
full_name: Shi, Siqi
last_name: Shi
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Yuhui
full_name: Chen, Yuhui
last_name: Chen
citation:
ama: Cao D, Shen X, Wang A, et al. Sharp kinetic acceleration potentials during
mediated redox catalysis of insulators. Research Square. doi:10.21203/rs.3.rs-750965/v1
apa: Cao, D., Shen, X., Wang, A., Yu, F., Wu, Y., Shi, S., … Chen, Y. (n.d.). Sharp
kinetic acceleration potentials during mediated redox catalysis of insulators.
Research Square. Research Square. https://doi.org/10.21203/rs.3.rs-750965/v1
chicago: Cao, Deqing, Xiaoxiao Shen, Aiping Wang, Fengjiao Yu, Yuping Wu, Siqi Shi,
Stefan Alexander Freunberger, and Yuhui Chen. “Sharp Kinetic Acceleration Potentials
during Mediated Redox Catalysis of Insulators.” Research Square. Research
Square, n.d. https://doi.org/10.21203/rs.3.rs-750965/v1.
ieee: D. Cao et al., “Sharp kinetic acceleration potentials during mediated
redox catalysis of insulators,” Research Square. Research Square.
ista: Cao D, Shen X, Wang A, Yu F, Wu Y, Shi S, Freunberger SA, Chen Y. Sharp kinetic
acceleration potentials during mediated redox catalysis of insulators. Research
Square, 10.21203/rs.3.rs-750965/v1.
mla: Cao, Deqing, et al. “Sharp Kinetic Acceleration Potentials during Mediated
Redox Catalysis of Insulators.” Research Square, Research Square, doi:10.21203/rs.3.rs-750965/v1.
short: D. Cao, X. Shen, A. Wang, F. Yu, Y. Wu, S. Shi, S.A. Freunberger, Y. Chen,
Research Square (n.d.).
date_created: 2021-08-31T12:54:16Z
date_published: 2021-08-18T00:00:00Z
date_updated: 2023-10-17T13:06:29Z
day: '18'
ddc:
- '541'
department:
- _id: StFr
doi: 10.21203/rs.3.rs-750965/v1
file:
- access_level: open_access
checksum: 1878e91c29d5769ed5a827b0b7addf00
content_type: application/pdf
creator: cchlebak
date_created: 2021-08-31T14:02:19Z
date_updated: 2021-08-31T14:02:19Z
file_id: '9979'
file_name: 2021_ResearchSquare_Cao.pdf
file_size: 1019662
relation: main_file
success: 1
file_date_updated: 2021-08-31T14:02:19Z
has_accepted_license: '1'
keyword:
- Catalysis
- Energy engineering
- Materials theory and modeling
language:
- iso: eng
month: '08'
oa: 1
oa_version: Preprint
page: '21'
publication: Research Square
publication_identifier:
eissn:
- 2693-5015
publication_status: submitted
publisher: Research Square
related_material:
record:
- id: '10813'
relation: later_version
status: public
status: public
title: Sharp kinetic acceleration potentials during mediated redox catalysis of insulators
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: preprint
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
year: '2021'
...
---
_id: '9980'
abstract:
- lang: eng
text: Insufficient understanding of the mechanism that reversibly converts sulphur
into lithium sulphide (Li2S) via soluble polysulphides (PS) hampers the realization
of high performance lithium-sulphur cells. Typically Li2S formation is explained
by direct electroreduction of a PS to Li2S; however, this is not consistent with
the size of the insulating Li2S deposits. Here, we use in situ small and wide
angle X-ray scattering (SAXS/WAXS) to track the growth and dissolution of crystalline
and amorphous deposits from atomic to sub-micron scales during charge and discharge.
Stochastic modelling based on the SAXS data allows quantification of the chemical
phase evolution during discharge and charge. We show that Li2S deposits predominantly
via disproportionation of transient, solid Li2S2 to form primary Li2S crystallites
and solid Li2S4 particles. We further demonstrate that this process happens in
reverse during charge. These findings show that the discharge capacity and rate
capability in Li-S battery cathodes are therefore limited by mass transport through
the increasingly tortuous network of Li2S / Li2S4 / carbon pores rather than electron
transport through a passivating surface film.
acknowledgement: "This project has received funding from the European Union’s Horizon
2020 research and innovation program under the Marie Skłodowska-Curie grant NanoEvolution,
grant agreement No 894042. The authors acknowledge TU Graz for support through the
Lead Project LP-03. Likewise, the use of SOMAPP Lab, a core facility supported by
the Austrian Federal Ministry of Education, Science and Research, the Graz University\r\n6
of Technology, the University of Graz, and Anton Paar GmbH is acknowledged. S.D.T,
A.V. and R.D. acknowledge the financial support by the Slovenian Research Agency
(ARRS) research core funding P2-0393. Furthermore, A.V. acknowledge the funding
from the Slovenian Research Agency, research project Z2-1863. S.A.F. is indebted
to IST Austria for support. "
article_processing_charge: No
author:
- first_name: Christian
full_name: Prehal, Christian
last_name: Prehal
- first_name: Sara Drvarič
full_name: Talian, Sara Drvarič
last_name: Talian
- first_name: Alen
full_name: Vizintin, Alen
last_name: Vizintin
- first_name: Heinz
full_name: Amenitsch, Heinz
last_name: Amenitsch
- first_name: Robert
full_name: Dominko, Robert
last_name: Dominko
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Vanessa
full_name: Wood, Vanessa
last_name: Wood
citation:
ama: Prehal C, Talian SD, Vizintin A, et al. Mechanism of Li2S formation and dissolution
in Lithium-Sulphur batteries. Research Square. doi:10.21203/rs.3.rs-818607/v1
apa: Prehal, C., Talian, S. D., Vizintin, A., Amenitsch, H., Dominko, R., Freunberger,
S. A., & Wood, V. (n.d.). Mechanism of Li2S formation and dissolution in Lithium-Sulphur
batteries. Research Square. https://doi.org/10.21203/rs.3.rs-818607/v1
chicago: Prehal, Christian, Sara Drvarič Talian, Alen Vizintin, Heinz Amenitsch,
Robert Dominko, Stefan Alexander Freunberger, and Vanessa Wood. “Mechanism of
Li2S Formation and Dissolution in Lithium-Sulphur Batteries.” Research Square,
n.d. https://doi.org/10.21203/rs.3.rs-818607/v1.
ieee: C. Prehal et al., “Mechanism of Li2S formation and dissolution in Lithium-Sulphur
batteries,” Research Square. .
ista: Prehal C, Talian SD, Vizintin A, Amenitsch H, Dominko R, Freunberger SA, Wood
V. Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries. Research
Square, 10.21203/rs.3.rs-818607/v1.
mla: Prehal, Christian, et al. “Mechanism of Li2S Formation and Dissolution in Lithium-Sulphur
Batteries.” Research Square, doi:10.21203/rs.3.rs-818607/v1.
short: C. Prehal, S.D. Talian, A. Vizintin, H. Amenitsch, R. Dominko, S.A. Freunberger,
V. Wood, Research Square (n.d.).
date_created: 2021-09-02T08:45:00Z
date_published: 2021-08-16T00:00:00Z
date_updated: 2021-12-03T10:35:42Z
day: '16'
ddc:
- '621'
department:
- _id: StFr
doi: 10.21203/rs.3.rs-818607/v1
keyword:
- Li2S
- Lithium Sulphur Batteries
- SAXS
- WAXS
language:
- iso: eng
main_file_link:
- open_access: '1'
url: https://www.researchsquare.com/article/rs-818607/v1
month: '08'
oa: 1
oa_version: Preprint
page: '21'
publication: Research Square
publication_status: submitted
status: public
title: Mechanism of Li2S formation and dissolution in Lithium-Sulphur batteries
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: preprint
user_id: 8b945eb4-e2f2-11eb-945a-df72226e66a9
year: '2021'
...
---
_id: '7847'
abstract:
- lang: eng
text: 'Water-in-salt electrolytes based on highly concentrated bis(trifluoromethyl)sulfonimide
(TFSI) promise aqueous electrolytes with stabilities nearing 3 V. However, especially
with an electrode approaching the cathodic (reductive) stability, cycling stability
is insufficient. While stability critically relies on a solid electrolyte interphase
(SEI), the mechanism behind the cathodic stability limit remains unclear. Here,
we reveal two distinct reduction potentials for the chemical environments of ''free''
and ''bound'' water and that both contribute to SEI formation. Free-water is reduced
~1V above bound water in a hydrogen evolution reaction (HER) and responsible for
SEI formation via reactive intermediates of the HER; concurrent LiTFSI precipitation/dissolution
establishes a dynamic interface. The free-water population emerges, therefore,
as the handle to extend the cathodic limit of aqueous electrolytes and the battery
cycling stability. '
article_processing_charge: No
article_type: original
author:
- first_name: Roza
full_name: Bouchal, Roza
last_name: Bouchal
- first_name: Zhujie
full_name: Li, Zhujie
last_name: Li
- first_name: Chandra
full_name: Bongu, Chandra
last_name: Bongu
- first_name: Steven
full_name: Le Vot, Steven
last_name: Le Vot
- first_name: Romain
full_name: Berthelot, Romain
last_name: Berthelot
- first_name: Benjamin
full_name: Rotenberg, Benjamin
last_name: Rotenberg
- first_name: Fréderic
full_name: Favier, Fréderic
last_name: Favier
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Mathieu
full_name: Salanne, Mathieu
last_name: Salanne
- first_name: Olivier
full_name: Fontaine, Olivier
last_name: Fontaine
citation:
ama: Bouchal R, Li Z, Bongu C, et al. Competitive salt precipitation/dissolution
during free‐water reduction in water‐in‐salt electrolyte. Angewandte Chemie
International Edition. 2020;59(37):15913-1591. doi:10.1002/anie.202005378
apa: Bouchal, R., Li, Z., Bongu, C., Le Vot, S., Berthelot, R., Rotenberg, B., …
Fontaine, O. (2020). Competitive salt precipitation/dissolution during free‐water
reduction in water‐in‐salt electrolyte. Angewandte Chemie International Edition.
Wiley. https://doi.org/10.1002/anie.202005378
chicago: Bouchal, Roza, Zhujie Li, Chandra Bongu, Steven Le Vot, Romain Berthelot,
Benjamin Rotenberg, Fréderic Favier, Stefan Alexander Freunberger, Mathieu Salanne,
and Olivier Fontaine. “Competitive Salt Precipitation/Dissolution during Free‐water
Reduction in Water‐in‐salt Electrolyte.” Angewandte Chemie International Edition.
Wiley, 2020. https://doi.org/10.1002/anie.202005378.
ieee: R. Bouchal et al., “Competitive salt precipitation/dissolution during
free‐water reduction in water‐in‐salt electrolyte,” Angewandte Chemie International
Edition, vol. 59, no. 37. Wiley, pp. 15913–1591, 2020.
ista: Bouchal R, Li Z, Bongu C, Le Vot S, Berthelot R, Rotenberg B, Favier F, Freunberger
SA, Salanne M, Fontaine O. 2020. Competitive salt precipitation/dissolution during
free‐water reduction in water‐in‐salt electrolyte. Angewandte Chemie International
Edition. 59(37), 15913–1591.
mla: Bouchal, Roza, et al. “Competitive Salt Precipitation/Dissolution during Free‐water
Reduction in Water‐in‐salt Electrolyte.” Angewandte Chemie International Edition,
vol. 59, no. 37, Wiley, 2020, pp. 15913–1591, doi:10.1002/anie.202005378.
short: R. Bouchal, Z. Li, C. Bongu, S. Le Vot, R. Berthelot, B. Rotenberg, F. Favier,
S.A. Freunberger, M. Salanne, O. Fontaine, Angewandte Chemie International Edition
59 (2020) 15913–1591.
date_created: 2020-05-14T21:00:30Z
date_published: 2020-09-07T00:00:00Z
date_updated: 2023-09-05T16:02:53Z
day: '07'
ddc:
- '540'
- '546'
department:
- _id: StFr
doi: 10.1002/anie.202005378
external_id:
isi:
- '000541488700001'
pmid:
- '32390281'
file:
- access_level: open_access
checksum: 7b6c2fc20e9b0ff4353352f7a7004e2d
content_type: application/pdf
creator: dernst
date_created: 2020-09-17T08:57:16Z
date_updated: 2020-09-17T08:57:16Z
file_id: '8400'
file_name: 2020_AngChemieINT_Buchal.pdf
file_size: 1966184
relation: main_file
success: 1
file_date_updated: 2020-09-17T08:57:16Z
has_accepted_license: '1'
intvolume: ' 59'
isi: 1
issue: '37'
language:
- iso: eng
month: '09'
oa: 1
oa_version: Published Version
page: 15913-1591
pmid: 1
publication: Angewandte Chemie International Edition
publication_identifier:
eissn:
- 1521-3773
issn:
- 1433-7851
publication_status: published
publisher: Wiley
quality_controlled: '1'
scopus_import: '1'
status: public
title: Competitive salt precipitation/dissolution during free‐water reduction in water‐in‐salt
electrolyte
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1
volume: 59
year: '2020'
...
---
_id: '7985'
abstract:
- lang: eng
text: The goal of limiting global warming to 1.5 °C requires a drastic reduction
in CO2 emissions across many sectors of the world economy. Batteries are vital
to this endeavor, whether used in electric vehicles, to store renewable electricity,
or in aviation. Present lithium-ion technologies are preparing the public for
this inevitable change, but their maximum theoretical specific capacity presents
a limitation. Their high cost is another concern for commercial viability. Metal–air
batteries have the highest theoretical energy density of all possible secondary
battery technologies and could yield step changes in energy storage, if their
practical difficulties could be overcome. The scope of this review is to provide
an objective, comprehensive, and authoritative assessment of the intensive work
invested in nonaqueous rechargeable metal–air batteries over the past few years,
which identified the key problems and guides directions to solve them. We focus
primarily on the challenges and outlook for Li–O2 cells but include Na–O2, K–O2,
and Mg–O2 cells for comparison. Our review highlights the interdisciplinary nature
of this field that involves a combination of materials chemistry, electrochemistry,
computation, microscopy, spectroscopy, and surface science. The mechanisms of
O2 reduction and evolution are considered in the light of recent findings, along
with developments in positive and negative electrodes, electrolytes, electrocatalysis
on surfaces and in solution, and the degradative effect of singlet oxygen, which
is typically formed in Li–O2 cells.
acknowledgement: "S.A.F. is indebted to the European Research Council (ERC) under
the European Union’s\r\nHorizon 2020 research and innovation programme (grant agreement
No 636069)."
article_processing_charge: No
article_type: review
author:
- first_name: WJ
full_name: Kwak, WJ
last_name: Kwak
- first_name: D
full_name: Sharon, D
last_name: Sharon
- first_name: C
full_name: Xia, C
last_name: Xia
- first_name: H
full_name: Kim, H
last_name: Kim
- first_name: LR
full_name: Johnson, LR
last_name: Johnson
- first_name: PG
full_name: Bruce, PG
last_name: Bruce
- first_name: LF
full_name: Nazar, LF
last_name: Nazar
- first_name: YK
full_name: Sun, YK
last_name: Sun
- first_name: AA
full_name: Frimer, AA
last_name: Frimer
- first_name: M
full_name: Noked, M
last_name: Noked
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: D
full_name: Aurbach, D
last_name: Aurbach
citation:
ama: 'Kwak W, Sharon D, Xia C, et al. Lithium-oxygen batteries and related systems:
Potential, status, and future. Chemical Reviews. 2020;120(14):6626-6683.
doi:10.1021/acs.chemrev.9b00609'
apa: 'Kwak, W., Sharon, D., Xia, C., Kim, H., Johnson, L., Bruce, P., … Aurbach,
D. (2020). Lithium-oxygen batteries and related systems: Potential, status, and
future. Chemical Reviews. American Chemical Society. https://doi.org/10.1021/acs.chemrev.9b00609'
chicago: 'Kwak, WJ, D Sharon, C Xia, H Kim, LR Johnson, PG Bruce, LF Nazar, et al.
“Lithium-Oxygen Batteries and Related Systems: Potential, Status, and Future.”
Chemical Reviews. American Chemical Society, 2020. https://doi.org/10.1021/acs.chemrev.9b00609.'
ieee: 'W. Kwak et al., “Lithium-oxygen batteries and related systems: Potential,
status, and future,” Chemical Reviews, vol. 120, no. 14. American Chemical
Society, pp. 6626–6683, 2020.'
ista: 'Kwak W, Sharon D, Xia C, Kim H, Johnson L, Bruce P, Nazar L, Sun Y, Frimer
A, Noked M, Freunberger SA, Aurbach D. 2020. Lithium-oxygen batteries and related
systems: Potential, status, and future. Chemical Reviews. 120(14), 6626–6683.'
mla: 'Kwak, WJ, et al. “Lithium-Oxygen Batteries and Related Systems: Potential,
Status, and Future.” Chemical Reviews, vol. 120, no. 14, American Chemical
Society, 2020, pp. 6626–83, doi:10.1021/acs.chemrev.9b00609.'
short: W. Kwak, D. Sharon, C. Xia, H. Kim, L. Johnson, P. Bruce, L. Nazar, Y. Sun,
A. Frimer, M. Noked, S.A. Freunberger, D. Aurbach, Chemical Reviews 120 (2020)
6626–6683.
date_created: 2020-06-19T08:42:47Z
date_published: 2020-03-05T00:00:00Z
date_updated: 2023-09-05T12:04:28Z
day: '05'
ddc:
- '540'
department:
- _id: StFr
doi: 10.1021/acs.chemrev.9b00609
external_id:
isi:
- '000555413600008'
pmid:
- '32134255'
file:
- access_level: open_access
checksum: 1a683353d46c5841c8bb2ee0a56ac7be
content_type: application/pdf
creator: sfreunbe
date_created: 2020-06-29T16:36:01Z
date_updated: 2020-07-14T12:48:06Z
file_id: '8060'
file_name: ChemRev_final.pdf
file_size: 8525678
relation: main_file
file_date_updated: 2020-07-14T12:48:06Z
has_accepted_license: '1'
intvolume: ' 120'
isi: 1
issue: '14'
language:
- iso: eng
month: '03'
oa: 1
oa_version: Submitted Version
page: 6626-6683
pmid: 1
publication: Chemical Reviews
publication_identifier:
eissn:
- 1520-6890
issn:
- 0009-2665
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: 'Lithium-oxygen batteries and related systems: Potential, status, and future'
type: journal_article
user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1
volume: 120
year: '2020'
...
---
_id: '8057'
abstract:
- lang: eng
text: Water-in-salt electrolytes based on highly concentrated bis(trifluoromethyl)sulfonimide
(TFSI) promise aqueous electrolytes with stabilities approaching 3 V. However,
especially with an electrode approaching the cathodic (reductive) stability, cycling
stability is insufficient. While stability critically relies on a solid electrolyte
interphase (SEI), the mechanism behind the cathodic stability limit remains unclear.
Here, we reveal two distinct reduction potentials for the chemical environments
of ‘free’ and ‘bound’ water and that both contribute to SEI formation. Free-water
is reduced ~1V above bound water in a hydrogen evolution reaction (HER) and responsible
for SEI formation via reactive intermediates of the HER; concurrent LiTFSI precipitation/dissolution
establishes a dynamic interface. The free-water population emerges, therefore,
as the handle to extend the cathodic limit of aqueous electrolytes and the battery
cycling stability.
article_processing_charge: No
article_type: original
author:
- first_name: Roza
full_name: Bouchal, Roza
last_name: Bouchal
- first_name: Zhujie
full_name: Li, Zhujie
last_name: Li
- first_name: Chandra
full_name: Bongu, Chandra
last_name: Bongu
- first_name: Steven
full_name: Le Vot, Steven
last_name: Le Vot
- first_name: Romain
full_name: Berthelot, Romain
last_name: Berthelot
- first_name: Benjamin
full_name: Rotenberg, Benjamin
last_name: Rotenberg
- first_name: Frederic
full_name: Favier, Frederic
last_name: Favier
- first_name: Stefan Alexander
full_name: Freunberger, Stefan Alexander
id: A8CA28E6-CE23-11E9-AD2D-EC27E6697425
last_name: Freunberger
orcid: 0000-0003-2902-5319
- first_name: Mathieu
full_name: Salanne, Mathieu
last_name: Salanne
- first_name: Olivier
full_name: Fontaine, Olivier
last_name: Fontaine
citation:
ama: Bouchal R, Li Z, Bongu C, et al. Competitive salt precipitation/dissolution
during free‐water reduction in water‐in‐salt electrolyte. Angewandte Chemie.
2020;132(37):16047-16051. doi:10.1002/ange.202005378
apa: Bouchal, R., Li, Z., Bongu, C., Le Vot, S., Berthelot, R., Rotenberg, B., …
Fontaine, O. (2020). Competitive salt precipitation/dissolution during free‐water
reduction in water‐in‐salt electrolyte. Angewandte Chemie. Wiley. https://doi.org/10.1002/ange.202005378
chicago: Bouchal, Roza, Zhujie Li, Chandra Bongu, Steven Le Vot, Romain Berthelot,
Benjamin Rotenberg, Frederic Favier, Stefan Alexander Freunberger, Mathieu Salanne,
and Olivier Fontaine. “Competitive Salt Precipitation/Dissolution during Free‐water
Reduction in Water‐in‐salt Electrolyte.” Angewandte Chemie. Wiley, 2020.
https://doi.org/10.1002/ange.202005378.
ieee: R. Bouchal et al., “Competitive salt precipitation/dissolution during
free‐water reduction in water‐in‐salt electrolyte,” Angewandte Chemie,
vol. 132, no. 37. Wiley, pp. 16047–16051, 2020.
ista: Bouchal R, Li Z, Bongu C, Le Vot S, Berthelot R, Rotenberg B, Favier F, Freunberger
SA, Salanne M, Fontaine O. 2020. Competitive salt precipitation/dissolution during
free‐water reduction in water‐in‐salt electrolyte. Angewandte Chemie. 132(37),
16047–16051.
mla: Bouchal, Roza, et al. “Competitive Salt Precipitation/Dissolution during Free‐water
Reduction in Water‐in‐salt Electrolyte.” Angewandte Chemie, vol. 132, no.
37, Wiley, 2020, pp. 16047–51, doi:10.1002/ange.202005378.
short: R. Bouchal, Z. Li, C. Bongu, S. Le Vot, R. Berthelot, B. Rotenberg, F. Favier,
S.A. Freunberger, M. Salanne, O. Fontaine, Angewandte Chemie 132 (2020) 16047–16051.
date_created: 2020-06-29T16:15:49Z
date_published: 2020-09-07T00:00:00Z
date_updated: 2023-09-05T15:47:50Z
day: '07'
ddc:
- '540'
- '541'
department:
- _id: StFr
doi: 10.1002/ange.202005378
file:
- access_level: open_access
checksum: 7dd0a56f6bd5de08ea75b1ec388c91bc
content_type: application/pdf
creator: dernst
date_created: 2020-09-17T08:59:43Z
date_updated: 2020-09-17T08:59:43Z
file_id: '8401'
file_name: 2020_AngChemieDE_Bouchal.pdf
file_size: 1904552
relation: main_file
success: 1
file_date_updated: 2020-09-17T08:59:43Z
has_accepted_license: '1'
intvolume: ' 132'
issue: '37'
language:
- iso: eng
month: '09'
oa: 1
oa_version: Published Version
page: 16047-16051
publication: Angewandte Chemie
publication_identifier:
eissn:
- 1521-3757
issn:
- 0044-8249
publication_status: published
publisher: Wiley
quality_controlled: '1'
scopus_import: '1'
status: public
title: Competitive salt precipitation/dissolution during free‐water reduction in water‐in‐salt
electrolyte
tmp:
image: /images/cc_by.png
legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
short: CC BY (4.0)
type: journal_article
user_id: c635000d-4b10-11ee-a964-aac5a93f6ac1
volume: 132
year: '2020'
...