Charging behavior of ZnMn2O4 and LiMn2O4 in a zinc- and lithium-ion battery: an ab initio study DOI Creative Commons
O.M. Sousa, L. V. C. Assali, M.V. Lalić

et al.

Journal of Physics Energy, Journal Year: 2024, Volume and Issue: 6(2), P. 025025 - 025025

Published: April 1, 2024

Abstract In the field of sustainable energy storage systems, zinc-ion batteries (ZIB) employing aqueous electrolytes have emerged as viable successors to widely used lithium-ion batteries, attributed their cost-effectiveness, environmental friendliness, and intrinsic safety features. Despite these advantages, performance ZIBs is significantly hindered by scarcity suitable cathode materials, positioning manganese zinc oxide (ZnMn 2 O 4 ) a potential solution. this study, we describe ZnMn (ZMO) compound focusing on its properties variations during Zn extraction battery applications. For sake comparison, also analyze same LiMn in tetragonal phase (TLMO), for first time, motivated recent discovery that substitution ions Li ZMO forms isostructural TLMO at room temperature. The study was conducted within density functional theory (DFT) framework, where structural, electronic, magnetic, electrochemical, spectroscopic are investigated under various conditions. Although both systems crystallize structures, they demonstrate distinct electronic magnetic due different oxidation states Mn. Computationally optimized lattice parameters align closely with experimental values. exhibits narrower band gap compared ZMO, indicating enhanced electrical conductivity. addition, presented lower diffusion barrier than better ionic To evaluate application materials technologies, further explored volume changes charging/discharging cycles, simulating or extraction. underwent significant contraction 5.8% upon complete removal, while experienced more pronounced 12.5% full removal. By adjusting ion levels, it possible reduce contractions, thereby approaching Voltage profiles, constructed from DFT-based simulation results, unveiled an average voltage 4.05 V TLMO, matching Furthermore, spectroscopy results provide insights into transitions validate computational findings, consolidating our understanding TLMO.

Language: Английский

Double-Layered Perovskite Oxyfluoride Cathodes with High Capacity Involving O–O Bond Formation for Fluoride-Ion Batteries DOI
Hidenori Miki, Kentaro Yamamoto,

Hiroyuki Nakaki

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3844 - 3853

Published: Jan. 9, 2024

Developing electrochemical high-energy storage systems is of crucial importance toward a green and sustainable energy supply. A promising candidate fluoride-ion batteries (FIBs), which can deliver much higher volumetric density than lithium-ion batteries. However, typical metal fluoride cathodes with conversion-type reactions cause low-rate capability. Recently, layered perovskite oxides oxyfluorides, such as LaSrMnO4 Sr3Fe2O5F2, have been reported to exhibit relatively high rate performance cycle stability compared reactions, but their discharge capacities (∼118 mA h/g) are lower those used in Here, we show that double-layered oxyfluoride La1.2Sr1.8Mn2O7−δF2 exhibits (de) intercalation two ions rock-salt slabs further excess the layer, leading reversible capacity 200 h/g. The additional leads formation O–O bond structure for charge compensation (i.e., anion redox). These results highlight oxyfluorides new class active materials construction high-performance FIBs.

Language: Английский

Citations

19
Does trapped O2 form in the bulk of LiNiO2 during charging? DOI Creative Commons
Mikkel Juelsholt, Jun Chen, Miguel A. Pérez‐Osorio

et al.

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(7), P. 2530 - 2540

Published: Jan. 1, 2024

The charge storage mechanism in LiNiO 2 Li-ion batteries is still under debate. Here, we show that trapped O forms during delithiation , accommodated by Ni vacancies, which form the layer.

Language: Английский

Citations

19
Jahn–Teller Distortions and Phase Transitions in LiNiO2: Insights from Ab Initio Molecular Dynamics and Variable-Temperature X-ray Diffraction DOI Creative Commons
Annalena R. Genreith‐Schriever, Alexandra Alexiu,

George Searle Phillips

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(5), P. 2289 - 2303

Published: Feb. 20, 2024

The atomistic structure of lithium nickelate (LiNiO2), the parent compound Ni-rich layered oxide cathodes for Li-ion batteries, continues to elude a comprehensive understanding. common consensus is that material exhibits local Jahn–Teller distortions dynamically reorient, resulting in time-averaged undistorted R3̅m structure. Through combination ab initio molecular dynamics (AIMD) simulations and variable-temperature X-ray diffraction (VT-XRD), we explore LiNiO2 as function temperature. Static are observed at low temperatures (T < 250 K) via AIMD simulations, followed by broad phase transition occurs between 350 K, leading highly dynamic, displacive high > K), which does not show four short two long bonds characteristic distortions. These transitions abrupt changes calculated pair distribution bond-length distortion index monoclinic lattice parameter ratio, amon/bmon, δ angle, fit quality an R3̅m-based structural refinement, peak sharpening peaks on heating, consistent with loss distorted domains. Between mixed-phase regime found where domains coexist. repeated change states this allows axes direction. pseudorotations Ni–O side effect onset transition. Antisite defects, involving Li ions Ni layer layer, pin temperatures, impeding cooperative ordering longer length scale.

Language: Английский

Citations

17
Identification of the dual roles of Al2O3 coatings on NMC811-cathodes via theory and experiment DOI Creative Commons
Richard L. B. Chen, Farheen N. Sayed, Hrishit Banerjee

et al.

Energy & Environmental Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Aluminium oxide coatings on Ni-rich layered materials have the dual functions of scavenging protic and acidic species from electrolyte, in stabilising surface oxygen against chemical oxidation electrolyte at high potentials.

Language: Английский

Citations

4
A Critical Analysis of Chemical and Electrochemical Oxidation Mechanisms in Li-Ion Batteries DOI Creative Commons
Evan Walter Clark Spotte‐Smith, Sudarshan Vijay,

Thea Bee Petrocelli

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(2), P. 391 - 400

Published: Jan. 4, 2024

Electrolyte decomposition limits the lifetime of commercial lithium-ion batteries (LIBs) and slows adoption next-generation energy storage technologies. A fundamental understanding electrolyte degradation is critical to rationally design stable energy-dense LIBs. To date, most explanations for at LIB positive electrodes have relied on ethylene carbonate (EC) being chemically oxidized by evolved singlet oxygen (1O2) or electrochemically oxidized. In this work, we apply density functional theory assess feasibility these mechanisms. We find that electrochemical oxidation unfavorable any potential reached during normal operation, predict previously reported reactions between EC 1O2 are kinetically limited room temperature. Our calculations suggest an alternative mechanism in which reacts with superoxide (O2–) and/or peroxide (O22–) anions. This work provides a new perspective motivates further studies understand reactivity electrodes.

Language: Английский

Citations

12
Elucidating Gas Evolution of Prussian White Cathodes for Sodium‐ion Battery Application: The Effect of Electrolyte and Moisture DOI Creative Commons
Sören L. Dreyer, Faduma M. Maddar, Aleksandr Kondrakov

et al.

Batteries & Supercaps, Journal Year: 2024, Volume and Issue: 7(4)

Published: Jan. 15, 2024

Abstract As global energy storage demand increases, sodium‐ion batteries are often considered as an alternative to lithium‐ion batteries. Hexacyanoferrate cathodes, commonly referred Prussian blue analogues (PBAs), of particular interest due their low‐cost synthesis and promising electrochemical response. However, because they consist ~50 wt% cyanide anions, a possible release highly toxic gases poses significant safety risk. Previously, we observed the evolution (CN) 2 during cycling via differential mass spectrometry (DEMS), but were unable determine root cause or mechanism. In this work, present systematical investigation gas white (PW) with different water content DEMS. While H is main detected, especially in hydrated PW overcharge (4.6 V vs. Na + /Na), CO depends on electrolyte conductive salt. The use oxidative NaClO 4 instead NaPF 6 leading for formation . Mass spectrometric evidence trace amounts HCN also found, much lower extent than , which dominant risk when using ‐containing electrolyte, despite being good model salt, not viable option commercial applications.

Language: Английский

Citations

9
Quantifying Electrochemical Degradation in Single-Crystalline LiNi0.8Mn0.1Co0.1O DOI Creative Commons
Ashok S. Menon, Nickil Shah, James A. Gott

et al.

PRX Energy, Journal Year: 2024, Volume and Issue: 3(1)

Published: Jan. 23, 2024

Using lab-based operando X-ray and post-mortem techniques, researchers visualize the origins of electrochemical capacity fade under high-voltage conditions in pilot line single-crystalline LiNi${}_{0.8}$Mn${}_{0.1}$Co${}_{0.1}$O${}_{2}$-graphite cells.

Language: Английский

Citations

9
Advances and perspectives in understanding the structure-redox relationship of layered Li-Co-Ni-Mn oxide cathode materials DOI
Zhenxing Wang, Linqing Li, Zhenhua Sun

et al.

Progress in Materials Science, Journal Year: 2024, Volume and Issue: 143, P. 101247 - 101247

Published: Feb. 9, 2024

Language: Английский

Citations

9
Probing Jahn–Teller Distortions and Antisite Defects in LiNiO2 with 7Li NMR Spectroscopy and Density Functional Theory DOI Creative Commons
Annalena R. Genreith‐Schriever,

Chloe Coates,

Katharina Märker

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(9), P. 4226 - 4239

Published: April 24, 2024

The long- and local-range structure electronic properties of the high-voltage lithium-ion cathode material for Li-ion batteries, LiNiO

Language: Английский

Citations

9
Influence of Carbonate Electrolyte Solvents on Voltage and Capacity Degradation in Li‐Rich Cathodes for Li‐ion Batteries DOI Creative Commons
Rui Wang, Bo Weng, Amoghavarsha Mahadevegowda

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(32)

Published: May 22, 2024

Abstract Lithium‐rich cobalt‐free cathodes, such as Li 1.2 Mn 0.6 Ni 0.2 O 2 (LMR), are promising next‐generation cathode materials because of their high energy density, cost efficiency, and sustainability. Nevertheless, LMRs suffer from degradation problems voltage decay during cycling. Different LMR surface doping coating strategies proposed to suppress with varying extents success. Here, the role played by different electrolyte solvents in oxygen loss is instead investigated. X‐ray absorption spectroscopy (XAS), electron (EELS), synchrotron XRD, online electrochemical mass spectrometry (OEMS) results show that ethylene carbonate (EC) leads accelerated surface. As a result, cycling cathodes EC‐free electrolytes pure EMC, improves capacity retention reduces decay. This approach provides new strategy increase stability which important for development more sustainable high‐performance batteries.

Language: Английский

Citations

9