---
_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.
    <i>Proceedings of the National Academy of Sciences</i>. 2021;118(14). doi:<a href="https://doi.org/10.1073/pnas.2021893118">10.1073/pnas.2021893118</a>
  apa: Prehal, C., Samojlov, A., Nachtnebel, M., Lovicar, L., Kriechbaum, M., Amenitsch,
    H., &#38; Freunberger, S. A. (2021). In situ small-angle X-ray scattering reveals
    solution phase discharge of Li–O2 batteries with weakly solvating electrolytes.
    <i>Proceedings of the National Academy of Sciences</i>. National Academy of Sciences.
    <a href="https://doi.org/10.1073/pnas.2021893118">https://doi.org/10.1073/pnas.2021893118</a>
  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.” <i>Proceedings of the National Academy of
    Sciences</i>. National Academy of Sciences, 2021. <a href="https://doi.org/10.1073/pnas.2021893118">https://doi.org/10.1073/pnas.2021893118</a>.
  ieee: C. Prehal <i>et al.</i>, “In situ small-angle X-ray scattering reveals solution
    phase discharge of Li–O2 batteries with weakly solvating electrolytes,” <i>Proceedings
    of the National Academy of Sciences</i>, 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.” <i>Proceedings
    of the National Academy of Sciences</i>, vol. 118, no. 14, e2021893118, National
    Academy of Sciences, 2021, doi:<a href="https://doi.org/10.1073/pnas.2021893118">10.1073/pnas.2021893118</a>.
  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: '8067'
abstract:
- lang: eng
  text: "With the lithium-ion technology approaching its intrinsic limit with graphite-based
    anodes, lithium metal is recently receiving renewed interest from the battery
    community as potential high capacity anode for next-generation rechargeable batteries.
    In this focus paper, we review the main advances in this field since the first
    attempts in the\r\nmid-1970s. Strategies for enabling reversible cycling and avoiding
    dendrite growth are thoroughly discussed, including specific applications in all-solid-state
    (polymeric and inorganic), Lithium-sulphur and Li-O2 (air) batteries. A particular
    attention is paid to review recent developments in regard of prototype manufacturing
    and current state-ofthe-art of these battery technologies with respect to the
    2030 targets of the EU Integrated Strategic Energy Technology Plan (SET-Plan)
    Action 7."
alternative_title:
- IST Austria Technical Report
article_processing_charge: No
author:
- first_name: Alberto
  full_name: Varzi, Alberto
  last_name: Varzi
- first_name: Katharina
  full_name: Thanner, Katharina
  last_name: Thanner
- first_name: Roberto
  full_name: Scipioni, Roberto
  last_name: Scipioni
- first_name: Daniele
  full_name: Di Lecce, Daniele
  last_name: Di Lecce
- first_name: Jusef
  full_name: Hassoun, Jusef
  last_name: Hassoun
- first_name: Susanne
  full_name: Dörfler, Susanne
  last_name: Dörfler
- first_name: Holger
  full_name: Altheus, Holger
  last_name: Altheus
- first_name: Stefan
  full_name: Kaskel, Stefan
  last_name: Kaskel
- first_name: Christian
  full_name: Prehal, Christian
  last_name: Prehal
- 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: Varzi A, Thanner K, Scipioni R, et al. <i>Current Status and Future Perspectives
    of Lithium Metal Batteries</i>. IST Austria doi:<a href="https://doi.org/10.15479/AT:ISTA:8067">10.15479/AT:ISTA:8067</a>
  apa: Varzi, A., Thanner, K., Scipioni, R., Di Lecce, D., Hassoun, J., Dörfler, S.,
    … Freunberger, S. A. (n.d.). <i>Current status and future perspectives of Lithium
    metal batteries</i>. IST Austria. <a href="https://doi.org/10.15479/AT:ISTA:8067">https://doi.org/10.15479/AT:ISTA:8067</a>
  chicago: Varzi, Alberto, Katharina Thanner, Roberto Scipioni, Daniele Di Lecce,
    Jusef Hassoun, Susanne Dörfler, Holger Altheus, Stefan Kaskel, Christian Prehal,
    and Stefan Alexander Freunberger. <i>Current Status and Future Perspectives of
    Lithium Metal Batteries</i>. IST Austria, n.d. <a href="https://doi.org/10.15479/AT:ISTA:8067">https://doi.org/10.15479/AT:ISTA:8067</a>.
  ieee: A. Varzi <i>et al.</i>, <i>Current status and future perspectives of Lithium
    metal batteries</i>. IST Austria.
  ista: Varzi A, Thanner K, Scipioni R, Di Lecce D, Hassoun J, Dörfler S, Altheus
    H, Kaskel S, Prehal C, Freunberger SA. Current status and future perspectives
    of Lithium metal batteries, IST Austria, 63p.
  mla: Varzi, Alberto, et al. <i>Current Status and Future Perspectives of Lithium
    Metal Batteries</i>. IST Austria, doi:<a href="https://doi.org/10.15479/AT:ISTA:8067">10.15479/AT:ISTA:8067</a>.
  short: A. Varzi, K. Thanner, R. Scipioni, D. Di Lecce, J. Hassoun, S. Dörfler, H.
    Altheus, S. Kaskel, C. Prehal, S.A. Freunberger, Current Status and Future Perspectives
    of Lithium Metal Batteries, IST Austria, n.d.
date_created: 2020-06-30T07:37:39Z
date_published: 2020-07-01T00:00:00Z
date_updated: 2023-08-22T09:20:36Z
day: '01'
ddc:
- '540'
department:
- _id: StFr
doi: 10.15479/AT:ISTA:8067
file:
- access_level: open_access
  checksum: d183ca1465a1cbb4f8db27875cd156f7
  content_type: application/pdf
  creator: dernst
  date_created: 2020-07-02T07:36:04Z
  date_updated: 2020-07-14T12:48:08Z
  file_id: '8076'
  file_name: 20200612_JPS_review_Li_metal_submitted.pdf
  file_size: 2612498
  relation: main_file
file_date_updated: 2020-07-14T12:48:08Z
has_accepted_license: '1'
keyword:
- Battery
- Lithium metal
- Lithium-sulphur
- Lithium-air
- All-solid-state
language:
- iso: eng
month: '07'
oa: 1
oa_version: Published Version
page: '63'
publication_identifier:
  issn:
  - 2664-1690
publication_status: submitted
publisher: IST Austria
related_material:
  record:
  - id: '8361'
    relation: later_version
    status: public
status: public
title: Current status and future perspectives of Lithium metal batteries
type: technical_report
user_id: 8b945eb4-e2f2-11eb-945a-df72226e66a9
year: '2020'
...