---
OA_place: publisher
OA_type: hybrid
PlanS_conform: '1'
_id: '21040'
abstract:
- lang: eng
  text: Formation during the first cycles of Li-rich layered oxide (LRLO) cathode
    materials consolidates the interphase and leads to structural changes that are
    decisive for long-term cyclability. However, the nature and effect of the changes
    are material-dependent and unknown for the important class of Co-free, Ni-poor
    LRLOs. Here, we analyze the processes during the tailored formation procedure
    of a typical class member, Li1.28Ni0.15Mn0.57O2, and demonstrate that it remarkably
    changes lattice composition and structure as a prerequisite for stable cycling.
    We combine electrochemistry, operando mass spectrometry, X-ray diffraction, and
    X-ray absorption spectroscopy with density functional theory simulations. Activation
    most prominently compresses the layer spacing along the c-axis and increases reversible
    structural breathing. The large capacity of ∼250 mAh g–1 originates from the Ni2+/Ni4+
    and O2–/O– redox couples. Electron exchange during O-redox is smeared over the
    entire anionic sublattice rather than localized on specific oxygen atomic sites.
    This redox mechanism is reversible without detrimental oxygen evolution, avoiding
    continued degradation common in conventional LRLOs. Sequential Ni- and O-redox
    during activation irreversibly distorts the coordination of the redox-inactive
    Mn4+ centers. This structural evolution of the MnO6 octahedra appears to enable
    the superior electrochemical performance of this LRLO phase. These findings define
    an activation pathway for the important class of Co-free, Ni-poor LRLOs, offering
    potential guidance for the rational design of high-performance, more sustainable
    cathode materials.
acknowledged_ssus:
- _id: M-Shop
- _id: LifeSc
acknowledgement: 'Elettra-Sincrotrone Trieste S.C.p.A. and its staff are acknowledged
  for providing synchrotron radiation beamtime and laboratory facilities, in particular
  the MCX and XAFS beamlines, where the XRD and XAS experiments have been carried
  out, supported by the projects number: 20217082, 20205109, and 20195014. This study
  was carried out within the MOST─Sustainable Mobility Center and received funding
  from the European Union Next-Generation EU (PIANO NAZIONALE DI RIPRESA E RESILIENZA
  (PNRR)─MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.4─D.D. 1033 17/06/2022, CN00000023).
  Moreover, the contribution of S.B. and A.C. to this study was carried out within
  the NEST─Network for Energy Sustainable Transition and received funding from the
  European Union Next-Generation EU (PNRR─MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.3─D.D.
  1561 11/10/2022, B53C22004070006). This manuscript reflects only the authors’ views
  and opinions, neither the European Union nor the European Commission can be considered
  responsible for them. Two of us, S.B. and S.A.F., would like to thank the Alistore
  ERI. L.S. received funds from the Ministry of Ecological Transition in the “Ricerca
  di Sistema Elettrico” framework. S.A.F. is indebted to ISTA for support. The Scientific
  Service Units of ISTA supported this research through resources provided by the
  Lab Support Facility and the Miba Machine Shop.'
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Matteo
  full_name: Busato, Matteo
  last_name: Busato
- first_name: Mariarosaria
  full_name: Tuccillo, Mariarosaria
  last_name: Tuccillo
- first_name: Arcangelo
  full_name: Celeste, Arcangelo
  last_name: Celeste
- first_name: Alessandro
  full_name: Tofoni, Alessandro
  last_name: Tofoni
- first_name: Laura
  full_name: Silvestri, Laura
  last_name: Silvestri
- first_name: Paola
  full_name: D’Angelo, Paola
  last_name: D’Angelo
- 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: Sergio
  full_name: Brutti, Sergio
  last_name: Brutti
citation:
  ama: Busato M, Tuccillo M, Celeste A, et al. Structural rearrangements of a Cobalt-free
    Lithium-rich layered oxide cathode during formation. <i>ACS Applied Energy Materials</i>.
    2026;9(1):686-697. doi:<a href="https://doi.org/10.1021/acsaem.5c03511">10.1021/acsaem.5c03511</a>
  apa: Busato, M., Tuccillo, M., Celeste, A., Tofoni, A., Silvestri, L., D’Angelo,
    P., … Brutti, S. (2026). Structural rearrangements of a Cobalt-free Lithium-rich
    layered oxide cathode during formation. <i>ACS Applied Energy Materials</i>. American
    Chemical Society. <a href="https://doi.org/10.1021/acsaem.5c03511">https://doi.org/10.1021/acsaem.5c03511</a>
  chicago: Busato, Matteo, Mariarosaria Tuccillo, Arcangelo Celeste, Alessandro Tofoni,
    Laura Silvestri, Paola D’Angelo, Stefan Alexander Freunberger, and Sergio Brutti.
    “Structural Rearrangements of a Cobalt-Free Lithium-Rich Layered Oxide Cathode
    during Formation.” <i>ACS Applied Energy Materials</i>. American Chemical Society,
    2026. <a href="https://doi.org/10.1021/acsaem.5c03511">https://doi.org/10.1021/acsaem.5c03511</a>.
  ieee: M. Busato <i>et al.</i>, “Structural rearrangements of a Cobalt-free Lithium-rich
    layered oxide cathode during formation,” <i>ACS Applied Energy Materials</i>,
    vol. 9, no. 1. American Chemical Society, pp. 686–697, 2026.
  ista: Busato M, Tuccillo M, Celeste A, Tofoni A, Silvestri L, D’Angelo P, Freunberger
    SA, Brutti S. 2026. Structural rearrangements of a Cobalt-free Lithium-rich layered
    oxide cathode during formation. ACS Applied Energy Materials. 9(1), 686–697.
  mla: Busato, Matteo, et al. “Structural Rearrangements of a Cobalt-Free Lithium-Rich
    Layered Oxide Cathode during Formation.” <i>ACS Applied Energy Materials</i>,
    vol. 9, no. 1, American Chemical Society, 2026, pp. 686–97, doi:<a href="https://doi.org/10.1021/acsaem.5c03511">10.1021/acsaem.5c03511</a>.
  short: M. Busato, M. Tuccillo, A. Celeste, A. Tofoni, L. Silvestri, P. D’Angelo,
    S.A. Freunberger, S. Brutti, ACS Applied Energy Materials 9 (2026) 686–697.
corr_author: '1'
date_created: 2026-01-25T23:01:40Z
date_published: 2026-01-12T00:00:00Z
date_updated: 2026-02-12T14:04:04Z
day: '12'
ddc:
- '540'
department:
- _id: StFr
doi: 10.1021/acsaem.5c03511
file:
- access_level: open_access
  checksum: 81272c19df41c696c1737168d3ea8c16
  content_type: application/pdf
  creator: dernst
  date_created: 2026-02-12T13:55:28Z
  date_updated: 2026-02-12T13:55:28Z
  file_id: '21222'
  file_name: 2026_AppliedEnergyMaterials_Busato.pdf
  file_size: 5977526
  relation: main_file
  success: 1
file_date_updated: 2026-02-12T13:55:28Z
has_accepted_license: '1'
intvolume: '         9'
issue: '1'
language:
- iso: eng
license: https://creativecommons.org/licenses/by/4.0/
month: '01'
oa: 1
oa_version: Published Version
page: 686-697
publication: ACS Applied Energy Materials
publication_identifier:
  eissn:
  - 2574-0962
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode
  during formation
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: 9
year: '2026'
...
---
_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. <i>ACS Applied Energy Materials</i>.
    2024;7(2):414-426. doi:<a href="https://doi.org/10.1021/acsaem.3c02223">10.1021/acsaem.3c02223</a>
  apa: Jethwa, R. B., Hey, D., Kerber, R. N., Bond, A. D., Wright, D. S., &#38; Grey,
    C. P. (2024). Exploring the landscape of heterocyclic quinones for redox flow
    batteries. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a
    href="https://doi.org/10.1021/acsaem.3c02223">https://doi.org/10.1021/acsaem.3c02223</a>
  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.” <i>ACS Applied Energy Materials</i>. American Chemical
    Society, 2024. <a href="https://doi.org/10.1021/acsaem.3c02223">https://doi.org/10.1021/acsaem.3c02223</a>.
  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,” <i>ACS
    Applied Energy Materials</i>, vol. 7, no. 2. American Chemical Society, pp. 414–426,
    2024.
  ista: Jethwa RB, Hey D, Kerber RN, Bond AD, Wright DS, Grey CP. 2024. Exploring
    the landscape of heterocyclic quinones for redox flow batteries. ACS Applied Energy
    Materials. 7(2), 414–426.
  mla: Jethwa, Rajesh B., et al. “Exploring the Landscape of Heterocyclic Quinones
    for Redox Flow Batteries.” <i>ACS Applied Energy Materials</i>, vol. 7, no. 2,
    American Chemical Society, 2024, pp. 414–26, doi:<a href="https://doi.org/10.1021/acsaem.3c02223">10.1021/acsaem.3c02223</a>.
  short: R.B. Jethwa, D. Hey, R.N. Kerber, A.D. Bond, D.S. Wright, C.P. Grey, ACS
    Applied Energy Materials 7 (2024) 414–426.
date_created: 2024-01-05T09:20:48Z
date_published: 2024-01-22T00:00:00Z
date_updated: 2025-09-04T11:36:32Z
day: '22'
ddc:
- '540'
department:
- _id: StFr
doi: 10.1021/acsaem.3c02223
ec_funded: 1
external_id:
  isi:
  - '001146733200001'
  pmid:
  - '38273966'
file:
- access_level: open_access
  checksum: 2841e86a041d249ac0df2531b7f9aec1
  content_type: application/pdf
  creator: dernst
  date_created: 2024-07-16T11:59:24Z
  date_updated: 2024-07-16T11:59:24Z
  file_id: '17262'
  file_name: 2024_ACSAppElecMaterials_Jethwa.pdf
  file_size: 5607177
  relation: main_file
  success: 1
file_date_updated: 2024-07-16T11:59:24Z
has_accepted_license: '1'
intvolume: '         7'
isi: 1
issue: '2'
keyword:
- Electrical and Electronic Engineering
- Materials Chemistry
- Electrochemistry
- Energy Engineering and Power Technology
- Chemical Engineering (miscellaneous)
language:
- iso: eng
main_file_link:
- open_access: '1'
  url: https://doi.org/10.1021/acsaem.3c02223
month: '01'
oa: 1
oa_version: Published Version
page: 414-426
pmid: 1
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: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '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: 317138e5-6ab7-11ef-aa6d-ffef3953e345
volume: 7
year: '2024'
...
---
OA_type: green
_id: '7467'
abstract:
- lang: eng
  text: Nanomaterials produced from the bottom-up assembly of nanocrystals may incorporate
    ∼1020–1021 cm–3 not fully coordinated surface atoms, i.e., ∼1020–1021 cm–3 potential
    donor or acceptor states that can strongly affect transport properties. Therefore,
    to exploit the full potential of nanocrystal building blocks to produce functional
    nanomaterials and thin films, a proper control of their surface chemistry is required.
    Here, we analyze how the ligand stripping procedure influences the charge and
    heat transport properties of sintered PbSe nanomaterials produced from the bottom-up
    assembly of colloidal PbSe nanocrystals. First, we show that the removal of the
    native organic ligands by thermal decomposition in an inert atmosphere leaves
    relatively large amounts of carbon at the crystal interfaces. This carbon blocks
    crystal growth during consolidation and at the same time hampers charge and heat
    transport through the final nanomaterial. Second, we demonstrate that, by stripping
    ligands from the nanocrystal surface before consolidation, nanomaterials with
    larger crystal domains, lower porosity, and higher charge carrier concentrations
    are obtained, thus resulting in nanomaterials with higher electrical and thermal
    conductivities. In addition, the ligand displacement leaves the nanocrystal surface
    unprotected, facilitating oxidation and chalcogen evaporation. The influence of
    the ligand displacement on the nanomaterial charge transport properties is rationalized
    here using a two-band model based on the standard Boltzmann transport equation
    with the relaxation time approximation. Finally, we present an application of
    the produced functional nanomaterials by modeling, fabricating, and testing a
    simple PbSe-based thermoelectric device with a ring geometry.
acknowledgement: This work was supported by the Spanish Ministerio de Economía y Competitividad
  through the project SEHTOP (ENE2016-77798-C4-3-R) and the Generalitat de Catalunya
  through the project 2017SGR1246. D.C. acknowledges support from Universidad Nacional
  de Colombia. Y.L. acknowledges funding from the European Union’s Horizon 2020 research
  and innovation programme under the Marie Sklodowska-Curie grant agreement no. 754411.
  M.I. acknowledges financial support from IST Austria.
article_processing_charge: No
article_type: original
author:
- first_name: Doris
  full_name: Cadavid, Doris
  last_name: Cadavid
- first_name: Silvia
  full_name: Ortega, Silvia
  last_name: Ortega
- first_name: Sergio
  full_name: Illera, Sergio
  last_name: Illera
- first_name: Yu
  full_name: Liu, Yu
  id: 2A70014E-F248-11E8-B48F-1D18A9856A87
  last_name: Liu
  orcid: 0000-0001-7313-6740
- first_name: Maria
  full_name: Ibáñez, Maria
  id: 43C61214-F248-11E8-B48F-1D18A9856A87
  last_name: Ibáñez
  orcid: 0000-0001-5013-2843
- first_name: Alexey
  full_name: Shavel, Alexey
  last_name: Shavel
- first_name: Yu
  full_name: Zhang, Yu
  last_name: Zhang
- first_name: Mengyao
  full_name: Li, Mengyao
  last_name: Li
- first_name: Antonio M.
  full_name: López, Antonio M.
  last_name: López
- first_name: Germán
  full_name: Noriega, Germán
  last_name: Noriega
- first_name: Oscar Juan
  full_name: Durá, Oscar Juan
  last_name: Durá
- first_name: M. A.
  full_name: López De La Torre, M. A.
  last_name: López De La Torre
- first_name: Joan Daniel
  full_name: Prades, Joan Daniel
  last_name: Prades
- first_name: Andreu
  full_name: Cabot, Andreu
  last_name: Cabot
citation:
  ama: Cadavid D, Ortega S, Illera S, et al. Influence of the ligand stripping on
    the transport properties of nanoparticle-based PbSe nanomaterials. <i>ACS Applied
    Energy Materials</i>. 2020;3(3):2120-2129. doi:<a href="https://doi.org/10.1021/acsaem.9b02137">10.1021/acsaem.9b02137</a>
  apa: Cadavid, D., Ortega, S., Illera, S., Liu, Y., Ibáñez, M., Shavel, A., … Cabot,
    A. (2020). Influence of the ligand stripping on the transport properties of nanoparticle-based
    PbSe nanomaterials. <i>ACS Applied Energy Materials</i>. American Chemical Society.
    <a href="https://doi.org/10.1021/acsaem.9b02137">https://doi.org/10.1021/acsaem.9b02137</a>
  chicago: Cadavid, Doris, Silvia Ortega, Sergio Illera, Yu Liu, Maria Ibáñez, Alexey
    Shavel, Yu Zhang, et al. “Influence of the Ligand Stripping on the Transport Properties
    of Nanoparticle-Based PbSe Nanomaterials.” <i>ACS Applied Energy Materials</i>.
    American Chemical Society, 2020. <a href="https://doi.org/10.1021/acsaem.9b02137">https://doi.org/10.1021/acsaem.9b02137</a>.
  ieee: D. Cadavid <i>et al.</i>, “Influence of the ligand stripping on the transport
    properties of nanoparticle-based PbSe nanomaterials,” <i>ACS Applied Energy Materials</i>,
    vol. 3, no. 3. American Chemical Society, pp. 2120–2129, 2020.
  ista: Cadavid D, Ortega S, Illera S, Liu Y, Ibáñez M, Shavel A, Zhang Y, Li M, López
    AM, Noriega G, Durá OJ, López De La Torre MA, Prades JD, Cabot A. 2020. Influence
    of the ligand stripping on the transport properties of nanoparticle-based PbSe
    nanomaterials. ACS Applied Energy Materials. 3(3), 2120–2129.
  mla: Cadavid, Doris, et al. “Influence of the Ligand Stripping on the Transport
    Properties of Nanoparticle-Based PbSe Nanomaterials.” <i>ACS Applied Energy Materials</i>,
    vol. 3, no. 3, American Chemical Society, 2020, pp. 2120–29, doi:<a href="https://doi.org/10.1021/acsaem.9b02137">10.1021/acsaem.9b02137</a>.
  short: D. Cadavid, S. Ortega, S. Illera, Y. Liu, M. Ibáñez, A. Shavel, Y. Zhang,
    M. Li, A.M. López, G. Noriega, O.J. Durá, M.A. López De La Torre, J.D. Prades,
    A. Cabot, ACS Applied Energy Materials 3 (2020) 2120–2129.
date_created: 2020-02-09T23:00:52Z
date_published: 2020-03-01T00:00:00Z
date_updated: 2026-07-28T12:54:00Z
day: '01'
ddc:
- '540'
department:
- _id: MaIb
doi: 10.1021/acsaem.9b02137
ec_funded: 1
external_id:
  isi:
  - '000526598300012'
file:
- access_level: open_access
  checksum: f23be731a766a480c77c962c1380315c
  content_type: application/pdf
  creator: dernst
  date_created: 2022-08-23T08:34:17Z
  date_updated: 2022-08-23T08:34:17Z
  file_id: '11942'
  file_name: 2020_ACSAppliedEnergyMat_Cadavid.pdf
  file_size: 6423548
  relation: main_file
  success: 1
file_date_updated: 2022-08-23T08:34:17Z
has_accepted_license: '1'
intvolume: '         3'
isi: 1
issue: '3'
language:
- iso: eng
month: '03'
oa: 1
oa_version: Accepted Version
page: 2120-2129
project:
- _id: 260C2330-B435-11E9-9278-68D0E5697425
  call_identifier: H2020
  grant_number: '754411'
  name: ISTplus - Postdoctoral Fellowships
publication: ACS Applied Energy Materials
publication_identifier:
  eissn:
  - 2574-0962
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Influence of the ligand stripping on the transport properties of nanoparticle-based
  PbSe nanomaterials
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 3
year: '2020'
...