| 1. |
- Retuerto, Maria, et al.
(författare)
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Pb2MnTeO6 Double Perovskite : An Antipolar Anti-ferromagnet
- 2016
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 55:9, s. 4320-4329
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Tidskriftsartikel (refereegranskat)abstract
- Pb2MnTeO6, a new double perovskite, was synthesized. Its crystal structure was determined by synchrotron X-ray and powder neutron diffraction. Pb2MnTeO6 is monoclinic (I2/m) at room temperature with a regular arrangement of all the cations in their polyhedra. However, when the temperature is lowered to similar to 120 K it undergoes a phase transition from I2/m to C2/c structure. This transition is accompanied by a displacement of the Pb atoms from the center of their polyhedra due to the 6s2 lone-pair electrons, together with a surprising off-centering of Mn2+ (d5) magnetic cations. This strong first-order phase transition is also evidenced by specific heat, dielectric, Raman, and infrared spectroscopy measurements. The magnetic characterizations indicate an anti-ferromagnetic (AFM) order below TN approximate to 20 K; analysis of powder neutron diffraction data confirms the magnetic structure with propagation vector k = (0 1 0) and collinear AFM spins. The observed jump in dielectric permittivity near similar to 150 K implies possible anti-ferroelectric behavior; however, the absence of switching suggests that Pb2MnTeO6 can only be antipolar. First-principle calculations confirmed that the crystal and magnetic structures determined are locally stable and that anti-ferroelectric switching is unlikely to be observed in Pb2MnTeO6.
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| 2. |
- Morozov, Anatolii V., et al.
(författare)
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Retardation of Structure Densification by Increasing Covalency in Li-Rich Layered Oxide Positive Electrodes for Li-Ion Batteries
- 2022
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 34:15, s. 6779-6791
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Tidskriftsartikel (refereegranskat)abstract
- Because of the outstanding discharge capacity provided by oxygen redox activity, Li-rich layered oxide positive electrode materials for Li-ion batteries attract tremendous attention. However, there is still no full consensus on the role that the ionocovalency of transition metal (TM)–oxygen (O) chemical bonding plays in the reversibility of the oxygen redox as well as on both local crystal and electronic structure transformations. Here, we managed to tune the cationic/anionic redox contributions to the overall electrochemical activity using the xLi2RuO3-(1 – x)Li1.2Ni0.2Mn0.6O2 solid solutions as a model system possessing the same crystal structure and morphology as Li-rich layered oxides. We conclusively traced the whole cascade of events from increasing the covalency of the TM–O bond, suppressing irreversible oxygen oxidation to the generation of the reduced Mn species toward retarding the structure “densification” in the Li-rich layered oxides. The results demonstrate that enhancing the degree of covalency of the TM–O bonding is vitally important for anchoring the reversibility of the charge compensation mechanism occurring through partial oxygen oxidation.
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| 3. |
- Li, Biao, et al.
(författare)
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Capturing dynamic ligand-to-metal charge transfer with a long-lived cationic intermediate for anionic redox
- 2022
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Ingår i: Nature Materials. - : Springer Nature. - 1476-1122 .- 1476-4660. ; 21:10, s. 1165-1174
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Tidskriftsartikel (refereegranskat)abstract
- Reversible anionic redox reactions represent a transformational change for creating advanced high-energy-density positive-electrode materials for lithium-ion batteries. The activation mechanism of these reactions is frequently linked to ligand-to-metal charge transfer (LMCT) processes, which have not been fully validated experimentally due to the lack of suitable model materials. Here we show that the activation of anionic redox in cation-disordered rock-salt Li1.17Ti0.58Ni0.25O2 involves a long-lived intermediate Ni3+/4+ species, which can fully evolve to Ni2+ during relaxation. Combining electrochemical analysis and spectroscopic techniques, we quantitatively identified that the reduction of this Ni3+/4+ species goes through a dynamic LMCT process (Ni3+/4+–O2− → Ni2+–On−). Our findings provide experimental validation of previous theoretical hypotheses and help to rationalize several peculiarities associated with anionic redox, such as cationic–anionic redox inversion and voltage hysteresis. This work also provides additional guidance for designing high-capacity electrodes by screening appropriate cationic species for mediating LMCT.
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| 4. |
- Li, Biao, et al.
(författare)
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Constructing “Li-rich Ni-rich” oxide cathodes for high-energy-density Li-ion batteries
- 2023
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Ingår i: Energy & Environmental Science. - : Royal Society of Chemistry. - 1754-5692 .- 1754-5706. ; 16:3, s. 1210-1222
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Tidskriftsartikel (refereegranskat)abstract
- The current exploration of high-energy-density cathode materials for Li-ion batteries is mainly concentrated on either so-called “Li-rich” or “Ni-rich” oxides. However, both are suffering from formidable practical challenges. Here, we combine these two concepts to obtain “Li-rich Ni-rich” oxides in pursuit of more practical high-energy-density cathodes. As a proof of concept, we synthesized an array of Li1+yNi(3−5y)/3Mo2y/3O2 oxides, whose structures were identified to be the coexistence of LiNiO2-rich and Li4MoO5-rich domains with the aid of XRD, TEM, and NMR techniques. Such an intergrowth structure of 5–20 nm size enables excellent mechanical and structural reversibility for the layered rock-salt LiNiO2-rich domain upon cycling thanks to the robust cubic rock-salt Li4MoO5-rich domain enabling an “epitaxial stabilization” effect. As a result, we achieved high capacities (>220 mA h g−1) with Ni contents as low as 80%; the Li1.09Ni0.85Mo0.06O2 member (y = 0.09) shows much improved cycling performances (91% capacity retention for 100 cycles at C/10) compared with pure LiNiO2. This work validates the feasibility of constructing Li-rich Ni-rich compounds in the form of intergrowing domains and hence unlocks vast possibilities for future cathode design.
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| 5. |
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| 6. |
- Li, Biao, et al.
(författare)
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Decoupling the roles of Ni and Co in anionic redox activity of Li-rich NMC cathodes
- 2023
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Ingår i: Nature Materials. - : Springer Nature. - 1476-1122 .- 1476-4660. ; 22:11, s. 1370-1379
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Tidskriftsartikel (refereegranskat)abstract
- Li[LixNiyMnzCo1−x−y−z]O2 (lithium-rich NMCs) are benchmark cathode materials receiving considerable attention due to the abnormally high capacities resulting from their anionic redox chemistry. Although their anionic redox mechanisms have been much investigated, the roles of cationic redox processes remain underexplored, hindering further performance improvement. Here we decoupled the effects of nickel and cobalt in lithium-rich NMCs via a comprehensive study of two typical compounds, Li1.2Ni0.2Mn0.6O2 and Li1.2Co0.4Mn0.4O2. We discovered that both Ni3+/4+ and Co4+, generated during cationic redox processes, are actually intermediate species for triggering oxygen redox through a ligand-to-metal charge-transfer process. However, cobalt is better than nickel in mediating the kinetics of ligand-to-metal charge transfer by favouring more transition metal migration, leading to less cationic redox but more oxygen redox, more O2 release, poorer cycling performance and more severe voltage decay. Our work highlights a compositional optimization pathway for lithium-rich NMCs by deviating from using cobalt to using nickel, providing valuable guidelines for future high-capacity cathode design.
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| 7. |
- Tsirlin, Alexander A., et al.
(författare)
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Short-range order of Br and three-dimensional magnetism in (CuBr) LaNb2O7
- 2012
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Ingår i: Physical Review B (Condensed Matter and Materials Physics). - 1098-0121. ; 85:21
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Tidskriftsartikel (refereegranskat)abstract
- We present a comprehensive study of the crystal structure, magnetic structure, and microscopic magnetic model of (CuBr)LaNb2O7, the Br analog of the spin-gap quantum magnet (CuCl) LaNb2O7. Despite similar crystal structures and spin lattices, the magnetic behavior and even peculiarities of the atomic arrangement in the Cl and Br compounds are very different. The high- resolution x-ray and neutron data reveal a split position of Br atoms in (CuBr) LaNb2O7. This splitting originates from two possible configurations developed by [CuBr] zigzag ribbons. While the Br atoms are locally ordered in the ab plane, their arrangement along the c direction remains partially disordered. The predominant and energetically more favorable configuration features an additional doubling of the c lattice parameter that was not observed in (CuCl) LaNb2O7. (CuBr) LaNb2O7 undergoes long-range antiferromagnetic ordering at T-N = 32 K, which is nearly 70% of the leading exchange coupling J4 similar or equal to 48 K. The Br compound does not show any experimental signatures of low-dimensional magnetism because the underlying spin lattice is three-dimensional. The coupling along the c direction is comparable to the couplings in the ab plane, even though the shortest Cu-Cu distance along c (11.69 angstrom) is three times larger than nearest-neighbor distances in the ab plane (3.55 angstrom). The stripe antiferromagnetic long-range order featuring columns of parallel spins in the ab plane and antiparallel spins along c is verified experimentally and confirmed by the microscopic analysis.
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| 8. |
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| 9. |
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| 10. |
- Yang, Tao, et al.
(författare)
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BiMnFe2O6, a polysynthetically twinned hcp MO structure
- 2010
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Ingår i: Chemical science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 1:6, s. 751-762
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Tidskriftsartikel (refereegranskat)abstract
- The most efficient use of spatial volume and the lowest potential energies in the metal oxide structures are based on cubic close packing (ccp) or hexagonal close packing (hcp) of anions with cations occupying the interstices. A promising way to tune the composition of close packed oxides and design new compounds is related to fragmenting the parent structure into modules by periodically spaced planar interfaces, such as twin planes at the unit cell scale. The unique crystal chemistry properties of cations with a lone electron pair, such as Bi3+ or Pb2+, when located at interfaces, enables them to act as "chemical scissors'', to help relieve configurational strain. With this approach, we synthesized a new oxide, BiMnFe2O6, where fragments of the hypothetical hcp oxygen-based MO structure (the NiAs structure type), for the first time, serve as the building modules in a complex transition metal oxide. Mn3+ and Fe3+ ions are randomly distributed in two crystallographically independent sites (M1 and M2). The structure consists of quasi two-dimensional blocks of the 2H hexagonal close packed MO structure cut along the (114) crystal plane of the hcp lattice and stacked along the c axis. The blocks are related by a mirror operation that allows BiMnFe2O6 to be considered as a polysynthetically twinned 2H hcp MO structure. The transition to an AFM state with an incommensurate spin configuration at similar to 212 K is established by Fe-57 Mossbauer spectroscopy, magnetic susceptibility, specific heat and low temperature powder neutron diffraction.
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| 11. |
- Yin, Wei, et al.
(författare)
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Structural evolution at the oxidative and reductive limits in the first electrochemical cycle of Li1.2Ni0.13Mn0.54Co0.13O2
- 2020
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 11:1
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Tidskriftsartikel (refereegranskat)abstract
- High-energy-density lithium-rich materials are of significant interest for advanced lithium-ion batteries, provided that several roadblocks, such as voltage fade and poor energy efficiency are removed. However, this remains challenging as their functioning mechanisms during first cycle are not fully understood. Here we enlarge the cycling potential window for Li1.2Ni0.13Mn0.54Co0.13O2 electrode, identifying novel structural evolution mechanism involving a structurally-densified single-phase A’ formed under harsh oxidizing conditions throughout the crystallites and not only at the surface, in contrast to previous beliefs. We also recover a majority of first-cycle capacity loss by applying a constant-voltage step on discharge. Using highly reducing conditions we obtain additional capacity via a new low-potential P” phase, which is involved into triggering oxygen redox on charge. Altogether, these results provide deeper insights into the structural-composition evolution of Li1.2Ni0.13Mn0.54Co0.13O2 and will help to find measures to cure voltage fade and improve energy efficiency in this class of material.
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